WO2022172448A1 - Two-component curing adhesive, laminated film, device for producing laminated film, and method for producing laminated film - Google Patents

Two-component curing adhesive, laminated film, device for producing laminated film, and method for producing laminated film Download PDF

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Publication number
WO2022172448A1
WO2022172448A1 PCT/JP2021/005515 JP2021005515W WO2022172448A1 WO 2022172448 A1 WO2022172448 A1 WO 2022172448A1 JP 2021005515 W JP2021005515 W JP 2021005515W WO 2022172448 A1 WO2022172448 A1 WO 2022172448A1
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Prior art keywords
film
polyol
polyisocyanate
composition
coating
Prior art date
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PCT/JP2021/005515
Other languages
French (fr)
Japanese (ja)
Inventor
健二 中村
厚美 佐野
智雄 大久保
雅裕 丹羽
Original Assignee
Dic株式会社
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Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to EP21777613.7A priority Critical patent/EP4071222A4/en
Priority to JP2021553276A priority patent/JP7136364B1/en
Priority to CN202180003072.XA priority patent/CN115413294A/en
Priority to US17/601,513 priority patent/US11525074B2/en
Priority to PCT/JP2021/005515 priority patent/WO2022172448A1/en
Priority to TW111104783A priority patent/TWI792909B/en
Publication of WO2022172448A1 publication Critical patent/WO2022172448A1/en

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    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
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    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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Definitions

  • the present invention relates to a two-component curing adhesive, a laminated film, a laminated film manufacturing apparatus, and a laminated film manufacturing method.
  • a laminate film in which two films are bonded together using an adhesive, and a two-component curing adhesive that uses a curing reaction between a polyisocyanate composition and a polyol composition is used as the adhesive.
  • a method for producing a laminated film using a two-component curing adhesive there are a method having a two-component mixed coating process that has been used for a long time and a method having a two-component separate coating process that has been attracting attention in recent years.
  • the polyisocyanate composition and the polyol composition are mixed to form a mixed liquid, and the two-liquid mixing coating step of applying this on the film, and the coating film formed on the film. and a step of forming an adhesive layer in which another film is laminated and cured.
  • a two-component separated coating comprising a first coating step of coating the polyisocyanate composition on the first film and a second coating step of coating the polyol composition on the second film.
  • Patent Documents 1 to 3 disclose solvent-free agent A that is liquid at room temperature applied to one adherend and solvent-free agent B that is liquid at room temperature and applied to the other adherend.
  • a two-part split-coat adhesive is described that initiates a curing reaction when it comes into contact with the adhesive.
  • the above agent A is mainly composed of a compound having an isocyanate group at both ends of the molecule
  • the above agent B is a compound having an amino group at both ends of the molecule and a compound having a tertiary amine in the molecule. and a tackifying resin are described.
  • the A agent is mainly composed of a compound having an isocyanate group at both molecular ends
  • the B agent is a two-component separate application type mainly composed of a compound having an amino group at both molecular ends.
  • a urethane adhesive is described.
  • the A agent is mainly composed of a compound having an isocyanate group at both ends of the molecule
  • the B agent is a two-liquid separate application type urethane system mainly composed of a compound having a hydroxyl group in the molecule. Adhesives are mentioned.
  • the cohesive force (initial cohesive force) immediately after adhesion may be insufficient.
  • the aging process may take a long time, or heating at about 40 to 60° C. may be required. For this reason, there was a possibility that the production efficiency of the laminated film would be lowered.
  • contact between the substrates occurs for the first time after the polyisocyanate composition and the polyol composition are each coated. For this reason, mixing of the composition and reaction between functional groups in the composition occur slowly, often resulting in insufficient initial cohesive strength.
  • misting stringing phenomenon
  • the adhesive scatters and adheres to manufacturing equipment and facilities, requiring periodic shutdown and cleaning.
  • the rotation speed of the rolls and the transport speed of the film are lowered in order to reduce the occurrence of misting, the production efficiency is lowered.
  • misting of the two-component curable adhesive tends to occur when the film transport speed is increased, which poses a problem. rice field.
  • the present invention has been made in view of the above circumstances, and is a two-component curing adhesive that uses a curing reaction between a polyisocyanate composition and a polyol composition, has excellent initial cohesive strength, and To provide a two-liquid curable adhesive that hardly causes misting even in a coating step.
  • the present invention is a two-component curable adhesive that uses a curing reaction between a polyisocyanate composition and a polyol composition, which hardly generates misting even when the step of coating on a film is performed, and has excellent initial cohesive strength.
  • An object of the present invention is to provide a laminated film which can be produced efficiently by using a two-component curing adhesive and which has excellent properties.
  • the present invention uses a two-component curable adhesive that is resistant to misting and has excellent initial cohesive strength, using a curing reaction between a polyisocyanate composition and a polyol composition, and a production method having a two-component separate application step.
  • An object of the present invention is to provide a laminated film manufacturing apparatus that can be suitably used when manufacturing a laminated film by a method.
  • the present invention uses a two-component curing adhesive that is resistant to misting and has excellent initial cohesive strength, using a curing reaction between a polyisocyanate composition and a polyol composition, to efficiently produce a laminated film. It aims at providing the manufacturing method of.
  • the present inventors have found that when using a two-component curing adhesive that uses a curing reaction between a polyisocyanate composition and a polyol composition, the misting that occurs in the process of applying it to the film In order to suppress the occurrence of this, and to increase the initial cohesive strength of the adhesive, we have made extensive studies. As a result, it was found that by using a polyisocyanate composition and a polyol composition having an elongational viscosity of 0.1 to 10 Pa s, the initial cohesive force can be improved and the occurrence of misting can be suppressed. I came up with That is, the present invention relates to the following matters.
  • the polyisocyanate composition (X) contains a polyisocyanate (A)
  • the polyol composition (Y) contains a polyol (B)
  • a two-component curing adhesive, wherein the polyisocyanate composition (X) and the polyol composition (Y) have extensional viscosities of 0.1 to 10 Pa ⁇ s.
  • [2] having an adhesive layer between the first film and the second film; A laminated film, wherein the adhesive layer is a cured product of the two-component curing adhesive according to [1].
  • a first coating section that applies a polyisocyanate composition (X) containing a polyisocyanate (A) and having an elongational viscosity of 0.1 to 10 Pa s to the first film; a second coating section for coating a second film with a polyol composition (Y) containing a polyol (B) and having an extensional viscosity of 0.1 to 10 Pa s;
  • An apparatus for producing a laminated film comprising a lamination device for laminating the surface of the first film coated with the polyisocyanate composition (X) and the surface of the second film coated with the polyol composition (Y).
  • the two-component curing adhesive of the present invention comprises a polyisocyanate composition (X) having an elongational viscosity of 0.1 to 10 Pa s and a polyol composition (Y) having an elongational viscosity of 0.1 to 10 Pa s. It is a two-component curing adhesive that uses a curing reaction with In the two-component curing adhesive of the present invention, the polyisocyanate composition (X) and the polyol composition (Y) have extensional viscosities of 0.1 to 10 Pa ⁇ s, and are excellent in initial cohesive strength. In addition, misting is less likely to occur even when the process of coating the film is performed.
  • the two-component curing adhesive of the present invention can be used when manufacturing a laminated film using a manufacturing method such as a manufacturing method having a two-component mixed coating process and a manufacturing method having a two-component separate coating process. It can be used preferably. In particular, it can be suitably used when a laminated film is continuously produced using a method having a two-part separate coating process.
  • the laminated film of the present invention has an adhesive layer between the first film and the second film, and the adhesive layer is made of the cured two-component curable adhesive of the present invention. Since the two-component curing adhesive of the present invention is excellent in initial cohesive strength, it is possible to shorten the aging time in the manufacturing process of the laminated film, widen the selection of processes, and efficiently manufacture the film. In addition, the laminated film of the present invention can be produced using the two-component curing adhesive of the present invention, which hardly causes misting even in the step of coating on the film. Therefore, the laminated film of the present invention can be efficiently manufactured using a manufacturing method including a two-component mixed coating process, a manufacturing method including a two-component separate coating process, and the like.
  • the first coating unit applies the polyisocyanate composition (X) having an extensional viscosity of 0.1 to 10 Pa s to the first film
  • the second coating The working part applies the polyol composition (Y) having an extensional viscosity of 0.1 to 10 Pa ⁇ s to the second film. Therefore, the laminated film manufacturing apparatus of the present invention can be suitably used when manufacturing a laminated film using the liquid-curable adhesive of the present invention by a manufacturing method having a two-liquid separate coating process.
  • the method for producing a laminated film of the present invention has a two-part separate coating step, and in the first coating step, the polyisocyanate composition (X) having an elongational viscosity of 0.1 to 10 Pa s is applied to the first film. Then, in the second coating step, the polyol composition (Y) having an extensional viscosity of 0.1 to 10 Pa ⁇ s is coated on the second film. Therefore, in the method for producing a laminated film of the present invention, a laminated film having excellent properties can be produced with high production efficiency using the two-component curing adhesive of the present invention having excellent initial cohesive strength.
  • the two-component curable adhesive of the present invention while suppressing the occurrence of misting due to applying the two-component curable adhesive on the film, it can be efficiently carried out at a continuously high film transport speed. Laminated films can be produced well.
  • FIG. 1 is a cross-sectional view showing an example of the laminated film according to this embodiment.
  • FIG. 2 is a front view of the laminated film manufacturing apparatus according to the present embodiment.
  • 3 is a front view showing a main part of a polyol coating section in the laminated film manufacturing apparatus shown in FIG. 2.
  • FIG. 4 is a front view showing a main part of a polyisocyanate coating section in the laminated film manufacturing apparatus shown in FIG. 2.
  • FIG. FIG. 5 is a front view for explaining another example of the manufacturing apparatus used for manufacturing the laminated film of this embodiment.
  • the two-component curable adhesive of the present embodiment is a two-component curable adhesive using a curing reaction between the polyisocyanate composition (X) and the polyol composition (Y).
  • the polyisocyanate composition (X) in the two-component curing adhesive of the present embodiment contains the polyisocyanate (A) and has an elongational viscosity of 0.1 to 10 Pa ⁇ s.
  • the polyol composition (Y) contains the polyol (B) and has an elongational viscosity of 0.1 to 10 Pa ⁇ s.
  • the polyisocyanate composition (X) may contain part of the polyol (B) contained in the two-component curing adhesive, if necessary.
  • the two-component curable adhesive of this embodiment cures through a chemical reaction between the isocyanate groups in the polyisocyanate composition (X) and the hydroxyl groups (or hydroxyl groups and amino groups) in the polyol composition (Y).
  • the two-component curing adhesive of the present embodiment has an elongational viscosity of 0.1 to 10 Pa ⁇ s for the polyisocyanate composition (X) and the polyol composition (Y), and is excellent in initial cohesive strength.
  • the extensional viscosity of the polyisocyanate composition (X) and the polyol composition (Y) is 0.1 to 10 Pa s
  • misting stringing phenomenon
  • the two-component curable adhesive of the present embodiment can be suitably used particularly when a laminated film is produced using a method having a two-component separate coating process in which misting is likely to occur.
  • the polyisocyanate composition (X) having an elongational viscosity of 0.1 to 10 Pa ⁇ s and the polyol composition (Y) having an elongational viscosity of 0.1 to 10 Pa ⁇ s have good reactivity.
  • the elongational viscosity of the polyisocyanate composition (X) is preferably 3 Pa s or more, more preferably 5 Pa s or more, more preferably 7 Pa s when a composition containing a prepolymer to be described later is used. It is more preferable that it is above.
  • the elongational viscosity of the polyol composition (Y) can more effectively suppress misting and has better reactivity with the polyisocyanate composition (X) to further improve the initial cohesive strength. ⁇ s or less is preferable, 5 Pa ⁇ s or less is more preferable, 3 Pa ⁇ s or less is even more preferable, and 2 Pa ⁇ s or less is particularly preferable. It is also preferable that the elongational viscosity of the polyol composition (Y) is 1 Pa ⁇ s or less.
  • Polyisocyanate composition (X) and polyol composition (Y) are preferably applied onto a substrate using a roll coater or gravure coater.
  • the polyisocyanate composition (X) and the polyol composition (Y) preferably have a constant elongational viscosity, preferably greater than 0.1 Pa s, and greater than 0.2 Pa s. is more preferable.
  • the elongational viscosity of the polyisocyanate composition (X) and the polyol composition (Y) is preferably more than 1 Pa ⁇ s.
  • the elongational viscosity of the polyisocyanate composition (X) can be controlled by adjusting the ratio of the low-viscosity material and the high-viscosity material contained in the materials (compounds) used in the polyisocyanate composition (X).
  • a person skilled in the art can grasp the viscosity of the material (compound) used for the polyisocyanate composition (X).
  • those skilled in the art can combine the materials (compounds) used in the polyisocyanate composition (X) and appropriately adjust the compounding ratio, within the scope of ordinary experiments, based on known techniques, A polyisocyanate composition (X) having an extensional viscosity within the desired range can be obtained.
  • the extensional viscosity of the polyol composition (Y) can be controlled by adjusting the ratio of the low-viscosity material and the high-viscosity material contained in the materials (compounds) used in the polyol composition (Y).
  • a person skilled in the art can grasp the viscosity of the material (compound) used for the polyol composition (Y). Further, those skilled in the art can combine the materials (compounds) used in the polyol composition (Y) and appropriately adjust the compounding ratio to achieve the desired result within the scope of ordinary experiments based on known techniques.
  • a polyol composition (Y) having an extensional viscosity within the range of can be obtained.
  • Polyisocyanate (A) As the polyisocyanate (A), known ones can be used without particular limitation.
  • Examples of the polyisocyanate (A) include tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate (hereinafter, diphenylmethane diisocyanate may be simply referred to as "MDI"), 2,2'-MDI, 4,4'-MDI, 1,5-naphthalene diisocyanate , aromatic polyisocyanates such as triphenylmethane triisocyanate; Aliphatic polyisocyanates such as xylylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), 1,3-(isocyanatomethyl)cyclohexane, 1,6-hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate ; Compounds in which
  • polystyrene resin examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1 ,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol , dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, and other chain aliphatic glycols; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and other alicyclic glycols; g
  • a polyester polyol (2) obtained by reacting a polyol such as the linear aliphatic glycol, alicyclic glycol, dimer diol, bisphenol, or polyether polyol with a polyvalent carboxylic acid; polyester polyol (3) obtained by reacting the trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid; A polyester obtained by reacting a polyol such as the chain aliphatic glycol, alicyclic glycol, dimer diol, bisphenol, or polyether polyol, the trifunctional or tetrafunctional aliphatic alcohol, and a polycarboxylic acid.
  • Polyester polyol (5) which is a polymer of hydroxy acids such as dimethylolpropionic acid and castor oil fatty acid; Castor oil, dehydrated castor oil, hydrogenated castor oil, castor oil-based polyols such as adducts of 5 to 50 moles of alkylene oxide of castor oil, and mixtures thereof.
  • Examples of the polyvalent carboxylic acid used for producing the polyester polyol (2), (3) or (4) include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, and fumaric acid.
  • non-cyclic aliphatic dicarboxylic acids such as; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; Anhydrides or ester-forming derivatives of aromatic or aromatic dicarboxylic acids; p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids, polybasic acids such as dimer acid is mentioned.
  • the polyisocyanate (A1) is preferred, and the polyisocyanate obtained by reacting the polyether polyol and the polyisocyanate is particularly preferred from the viewpoint of wettability. Furthermore, it is preferable to use a polyol having a polypropylene skeleton as the polyol component to be reacted with the polyisocyanate, since the polyisocyanate (A1) has a low viscosity and is easy to handle at low temperatures.
  • the polyol component to be reacted with the polyisocyanate has a number average molecular weight (Mn) of 300 to 5,000, more preferably 350 to 3,000.
  • Ether polyols are preferably used.
  • the proportion of polyether polyol having a number average molecular weight (Mn) of 300 to 5,000 in the polyol component is preferably 50% by mass or more.
  • the total polyol component may be a polyether polyol having a number average molecular weight (Mn) of 300-5,000.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) under the following conditions.
  • Measuring device HLC-8320GPC manufactured by Tosoh Corporation Column; TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by Tosoh Corporation Detector; RI (differential refractometer) Data processing; Multi-station GPC-8020modelII manufactured by Tosoh Corporation Measurement conditions; column temperature 40°C Solvent; tetrahydrofuran flow rate; 0.35 ml/min standard; monodisperse polystyrene sample; 0.2% by mass of tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 ⁇ l)
  • the polyisocyanate to be reacted with the polyol component preferably contains an aromatic polyisocyanate because of its excellent reactivity with the polyamine (C) described later.
  • the amount of the aromatic polyisocyanate to be blended is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, for 100 parts by mass of the total charged amount for synthesizing the polyisocyanate (A1).
  • the upper limit of the amount of the aromatic polyisocyanate compounded is preferably 60 parts by mass or less, more preferably 55 parts by mass or less.
  • polyisocyanate to be reacted with the polyol component, it is preferable to use at least one of aliphatic polyisocyanate and aliphatic polyisocyanate derivative together with aromatic polyisocyanate from the viewpoint of storage stability.
  • the reaction ratio of the polyisocyanate and the polyol component in the polyisocyanate (A1) is such that the equivalent ratio [isocyanate group/hydroxyl group] between the isocyanate group in the polyisocyanate and the hydroxyl group in the polyol component is 1.5 to 5.0. A range is preferred.
  • the polyisocyanate (A) employing such a polyisocyanate (A1) has an appropriate viscosity of the polyisocyanate composition (X) containing it, and the coating property is improved, and the polyisocyanate (A ) is preferable because the cohesive force of the coating film made of the two-component curing adhesive containing is improved.
  • the polyisocyanate (A) preferably has a weight average molecular weight (Mw) in the range of 100 to 10,000 from the viewpoint of shortening the aging time and ensuring proper packaging properties. A range is more preferred.
  • Mw weight average molecular weight
  • the polyisocyanate (A) is the polyisocyanate (A1), it preferably has a weight average molecular weight (Mw) in the range of 300 to 10,000.
  • the polyisocyanate (A) preferably has an isocyanate content of 5 to 20% by mass.
  • the polyisocyanate composition (X) containing such a polyisocyanate (A) is preferable because it has an appropriate resin viscosity and is excellent in coatability.
  • the isocyanate content of polyisocyanate (A) is a value determined by a titration method using di-n-butylamine.
  • polyol (B) examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6 - hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol , 1,4-cyclohexanedimethanol, glycols such as triethylene glycol;
  • trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, and pentaerythritol; bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F; dimer diols;
  • polyester polyol (2) obtained by reacting a bifunctional polyol such as the glycol, dimer diol, or bisphenol with a polyvalent carboxylic acid
  • polyester polyol (3) obtained by reacting the trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid
  • a polyester polyol (4) obtained by reacting a bifunctional polyol, the trifunctional or tetrafunctional aliphatic alcohol, and a polyvalent carboxylic acid
  • Polyester polyol (5) which is a polymer of hydroxy acids such as dimethylolpropionic acid and castor oil fatty acid
  • Polyester polyether polyols obtained by reacting the polyester polyols (1) to (5), the polyether polyols, and an aromatic or aliphatic polyisocyanate
  • polyester polyurethane polyols obtained by polymerizing the polyester polyols (1) to (5) with aromatic or aliphatic polyisocyanates
  • Castor oil dehydrated castor oil, hydrogenated castor oil,
  • Examples of the polyvalent carboxylic acid used for producing the polyester polyol (2), (3) or (4) include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, and fumaric acid.
  • a tertiary amine compound having a plurality of hydroxyl groups may be used as the polyol (B).
  • a tertiary amine compound having a plurality of hydroxyl groups not only cures when the hydroxyl groups react with the polyisocyanate (A), but also functions as a curing accelerator because the amine structure accelerates the curing reaction.
  • the number of hydroxyl groups is 2 or more, preferably 2 to 6.
  • a tertiary amine compound having a plurality of hydroxyl groups may have one or more tertiary amino groups, preferably one or two.
  • tertiary amine compounds having a plurality of hydroxyl groups include polypropylene glycol ethylene diamine ether, tri(1,2-polypropylene glycol) amine, N-ethyldiethanolamine, N-methyl-N-hydroxyethyl-N-hydroxy ethoxyethylamine, pentakishydroxypropyldiethylenetriamine, tetrakishydroxypropylethylenediamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, triethanolamine, triethanolamine propoxylated and the like.
  • a commercially available product may be used as the tertiary amine compound having multiple hydroxyl groups.
  • Examples of commercially available products include EDP-300 manufactured by ADEKA Corporation, ED-500 and TE-360 manufactured by Kokuto Kako, and VORANOL TM800 Polyol manufactured by DOW.
  • the mixing ratio of the polyol other than the tertiary amine compound in the polyol (B) and the tertiary amine compound (polyol other than the tertiary amine compound/ The tertiary amine compound (mass ratio)) is preferably from 100/5 to 100/70, more preferably from 100/10 to 100/70.
  • Polyol (B) preferably contains a polyol having a polyether skeleton, and more preferably contains a polyol having a polypropylene skeleton.
  • a polyol (B) has a viscosity that enables coating at a temperature of 25° C. to 60° C. even if it is a non-solvent type.
  • the two-component curing adhesive containing such a polyol (B) is preferable because it exhibits excellent adhesion strength to metal oxides such as silica and/or alumina, metals such as aluminum, and resin films.
  • the content of the polyol having a polyether skeleton is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass, based on the total amount of the polyol (B) from the viewpoint of coatability. It is more preferable to be above.
  • the upper limit of the content of the polyol having a polyether skeleton is not particularly limited, and the total amount of the polyol (B) may be a polyol having a polyether skeleton. From the viewpoint, it is preferably 95% by mass or less.
  • Polyol (B) is castor oil, dehydrated castor oil, hydrogenated castor oil that is a hydrogenated product of castor oil, and 5 to 50 moles of alkylene oxide added to castor oil, from the viewpoint of the initial cohesive strength and coatability of the two-component curing adhesive. It preferably contains at least one castor oil-based compound selected from the group consisting of castor oil-based polyols such as castor oil-based polyols. These castor oil-based compounds are preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass or more, and 20% by mass of the total amount of polyol (B). It is more preferable to be above. Also, the upper limit of the castor oil-based compound is not particularly limited, and the total amount of the polyol (B) may be a castor oil-based compound, but from the viewpoint of coatability, it is preferably 95% by mass or less.
  • the polyol (B) may contain a highly reactive low-molecular-weight polyol (liquid at room temperature and having a molecular weight of about 150 or less). By containing such a low-molecular-weight polyol, the reaction with the polyisocyanate (A) can be accelerated. On the other hand, if the amount of the low-molecular-weight polyol is too large, the reaction with the polyisocyanate (A) may be too fast. Therefore, the content of the low-molecular-weight polyol is preferably 5% by mass or less, more preferably 3% by mass or less, of the polyol (B).
  • the viscosity of the polyol (B) is 400 to 5000, so the coatability is improved, and the cohesive force of the two-component curing adhesive is improved, which is preferable. .
  • the hydroxyl value of the polyol (B) is preferably 50 mgKOH/g or more and 300 mgKOH/g or less, more preferably 100 mgKOH/g or more and 250 mgKOH/g or less.
  • the hydroxyl value of the polyol (B) can be measured by the hydroxyl value measuring method described in JIS-K0070.
  • the polyol composition (Y) preferably contains a polyamine (C).
  • Polyamine (C) functions as a curing accelerator.
  • the polyamine (C) known ones can be used without particular limitation.
  • Polyamine (C) has two amino groups ( NH2 group, NHR group (R represents an alkyl group)) in the molecule in order to maintain the toughness of the coating film made of a two-component curing adhesive. It is desirable that the compound has the above.
  • polyamine (C) examples include methylenediamine, ethylenediamine, isophoronediamine, 3,9-dipropanamine-2,4,8,10-tetraoxapyrodundecane, lysine, phenylenediamine, 2,2,4- trimethylhexamethylenediamine, tolylenediamine, hydrazine, piperazine, hexamethylenediamine, propylenediamine, dicyclohexylmethane-4,4-diamine, 2-hydroxyethylethylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylene diamine, 2-hydroxypropylethylenediamine, or di-2-hydroxypropylethylenediamine, poly(propylene glycol) diamine, poly(propylene glycol) triamine, poly(propylene glycol) tetraamine, 1,2-diaminopropane, 1,3-diamino propane,
  • 1,4-diaminobutane 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, etc.
  • benzyl amine diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, trimethylhexamethylenediamine, etc., tetra(aminomethyl)methane, tetrakis ( 2-aminoethylaminomethyl)methane, 1,3-bis(2′-aminoethylamino)propane, triethylene-bis(trimethylene)hexamine, bis(3-aminoethy
  • polyamine (C) it is preferable to use a polyetheramine having a polyether structure in the main chain in order to maintain the flexibility of the coating film composed of the two-component curing adhesive.
  • These polyamines (C) may be used alone or in combination of two or more.
  • a commercially available product may be used as the polyamine (C).
  • Commercially available products include EC-310 and EC-303 manufactured by BASF.
  • the functional group in the polyisocyanate composition (X) (the isocyanate group of the polyisocyanate (A)) and the functional group in the polyol composition (Y) (the hydroxyl group of the polyol (B), the amino group of the polyamine (C), group) molar ratio [isocyanate group / (hydroxyl group + amino group)] is preferably 0.5 to 5.0, and from the viewpoint of the adhesive performance of the two-component curing adhesive, 1.0 to 3.0 is more desirable.
  • the ratio of the polyol (B) and the polyamine (C) in the polyol composition (Y) is such that the molar ratio [amino group/hydroxyl group] of the amino group derived from the polyamine (C) and the hydroxyl group derived from the polyol (B) is 0. .001 to 2.0 is desirable, and from the viewpoint of achieving both the adhesive strength of the two-part curing adhesive, the processed appearance, and the practicality of workability, the range of 0.1 to 1.0 is more preferable. preferable.
  • the above molar ratio is 0.001 or more, the workability of the laminated film produced using the two-component curing adhesive becomes favorable.
  • the molar ratio is 2.0 or less, the adhesion strength of the two-component curing adhesive becomes favorable.
  • the two-component curable adhesive of the present embodiment can be used as a solventless adhesive, but the two-component curable adhesive of the present embodiment may contain a solvent if necessary.
  • the "solvent” refers to a highly soluble organic solvent capable of dissolving the polyisocyanate composition (X) and/or the polyol composition (Y).
  • solvent-free refers to not containing these highly soluble organic solvents.
  • solvents include toluene, xylene, methylene chloride, tetrahydrofuran, methanol, ethanol, isopropyl alcohol, methyl acetate, ethyl acetate, n-butyl acetate, acetone, and methyl ethyl ketone (MEK). , cyclohexanone, n-hexane, cyclohexane, and the like.
  • solvents include toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, and ethyl acetate are particularly highly soluble organic solvents.
  • the two-component curable adhesive of this embodiment can be used by diluting it with a solvent so as to obtain the desired viscosity when it is required to lower the viscosity.
  • a solvent may be used to dilute either one of the polyisocyanate composition (X) or the polyol composition (Y), or both.
  • organic solvents examples include methanol, ethanol, isopropyl alcohol, methyl acetate, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, Examples include toluene, xylene, n-hexane, cyclohexane and the like.
  • ethyl acetate and/or methyl ethyl ketone (MEK) it is preferable to use ethyl acetate, from the viewpoint of the solubility of the polyisocyanate composition (X) and the polyol composition (Y).
  • MEK methyl ethyl ketone
  • the content of the organic solvent in the two-component curing adhesive of the present embodiment can be appropriately determined according to the required viscosity, and can be, for example, 20 to 50% by mass.
  • the two-component curing adhesive of this embodiment may contain a catalyst.
  • the catalyst may be contained in either one of the polyisocyanate composition (X) and the polyol composition (Y), or may be contained in both.
  • the catalyst generally has a high reactivity with the polyisocyanate composition, and after the polyisocyanate composition (X) and the polyol composition (Y) are brought into contact with each other, the catalyst is effectively activated. It is preferably contained only in (Y).
  • the catalyst may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) during coating of the two-component curing adhesive.
  • the two-component curing adhesive contains a catalyst
  • the curing of the two-component curing adhesive is accelerated, and the laminate film produced using the two-component curing adhesive is exposed to harmful low-grade compounds such as aromatic amines. Elution of molecular chemicals can be suppressed. That is, the catalyst also works as a curing accelerator like polyamine (C) and the like.
  • the catalyst is not particularly limited as long as it promotes the urethanization reaction between the polyisocyanate composition (X) and the polyol composition (Y).
  • catalysts that can be used include metal-based catalysts, amine-based catalysts, diazabicycloundecene (DBU), aliphatic cyclic amide compounds, and titanium chelate complexes.
  • Metal-based catalysts include metal complex-based catalysts, inorganic metal-based catalysts, and organic metal-based catalysts.
  • the metal complex catalyst from the group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum) and Co (cobalt) Acetylacetonate salts of selected metals and the like are included. Specific examples include iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, and zirconia acetylacetonate.
  • iron acetylacetonate Fe(acac) 3
  • manganese acetylacetonate Mn(acac) 2
  • Organometallic catalysts include stannus diacetate, stannus dioctoate, stannus dioleate, stannus dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, nickel octylate, nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate, bismuth naphthenate, bismuth neodecanoate, zinc neodecanoate and the like.
  • preferred organometallic catalysts are stannous dioctoate, dibutyltin dilaurate, bismuth neodecanoate, zinc neodecanoate, or mixtures thereof.
  • amine-based catalysts examples include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, and 2-methylquinuclidine.
  • triethylenediamine and/or 2-methyltriethylenediamine are preferably used as the amine-based catalyst because of their excellent catalytic activity and industrial availability.
  • tertiary amine catalysts include N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'',N ′′-pentamethyldiethylenetriamine, N,N,N′,N′′,N′′-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N′,N′′,N′′-pentamethyldipropylenetriamine, N, N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N'-(2-hydroxy ethyl)ethylenediamine, N,N-dimethyl-N'-(2-hydroxyethyl)propanediamine, bis(dimethylaminoprop
  • aliphatic cyclic amide compounds used as catalysts include ⁇ -valerolactam, ⁇ -caprolactam, ⁇ -enanthrolactam, ⁇ -capryllactam and ⁇ -propiolactam.
  • ⁇ -caprolactam can more effectively accelerate the curing of two-component curing adhesives.
  • the content of the catalyst in the two-component curing adhesive of this embodiment is not particularly limited, and can be a known amount.
  • the content of the catalyst can be, for example, 0.001 to 5.0% by mass with respect to the total solid content of the two-component curing adhesive.
  • the two-component curing adhesive of this embodiment may contain an adhesion promoter.
  • the adhesion promoter may be contained in either one of the polyisocyanate composition (X) and the polyol composition (Y), or may be contained in both. Since the adhesion promoter has high reactivity with the polyisocyanate composition (X), it is preferred to act after the polyisocyanate composition (X) and the polyol composition (Y) are brought into contact with each other. Therefore, the adhesion promoter is preferably contained only in the polyol composition (Y).
  • the adhesion promoter may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) during coating of the two-component curing adhesive. Examples of adhesion promoters include silane coupling agents, titanate-based coupling agents, aluminum-based coupling agents, epoxy resins, and the like.
  • Silane coupling agents include, for example, ⁇ -aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl)- ⁇ -aminopropyltrimethoxysilane, Aminosilanes such as N- ⁇ (aminoethyl)- ⁇ -aminopropyltrimethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane; ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycides epoxysilanes such as xypropyltrimethoxysilane and ⁇ -glycidoxypropyltriethoxysilane; vinylsilanes such as vinyltris( ⁇ -methoxyethoxy)silane, vinyltrie
  • Titanate-based coupling agents include, for example, tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, tetrastearoxy Titanium etc. can be mentioned.
  • aluminum-based coupling agents include acetoalkoxyaluminum diisopropylate.
  • epoxy resin generally commercially available epi-bis type, novolac type, ⁇ -methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, polyvalent carboxylic acid ester type, aminoglycidyl type, resorcinol type, and other epoxy resins.
  • the content of the adhesion promoter in the two-component curing adhesive of this embodiment is not particularly limited, and can be a known amount.
  • the content of the adhesion promoter can be, for example, 0 to 50% by mass with respect to the total solid content of the two-component curing adhesive.
  • the two-component curing adhesive of the present embodiment may be used in combination with a pigment, if necessary.
  • the pigment may be contained in either one of the polyisocyanate composition (X) and the polyol composition (Y), or may be contained in both.
  • the pigment may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) during coating of the two-component curing adhesive.
  • the pigment is not particularly limited, and includes various pigments.
  • pigments include extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, and metal powders described in the 1970 edition of Handbook of Paint Materials (edited by the Japan Paint Manufacturers Association).
  • organic pigments such as pigments, luminescent pigments and pearlescent pigments, inorganic pigments, and plastic pigments.
  • organic pigments examples include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow and Laked 4R; soluble azo pigments such as Laked C, Carmine 6B and Bordeaux 10; various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green.
  • insoluble azo pigments such as Benzidine Yellow, Hansa Yellow and Laked 4R
  • soluble azo pigments such as Laked C, Carmine 6B and Bordeaux 10
  • various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green.
  • Pigments various chlorine dyeing lakes such as rhodamine lake and methyl violet lake; various mordant pigments such as quinoline lake and fast sky blue; various vat dyes such as anthraquinone pigments, thioindigo pigments and perinone pigments dye-based pigments; various quinacridone-based pigments such as Cincasia Red B; various dioxazine-based pigments such as dioxazine violet; various condensed azo pigments such as chromophtal;
  • inorganic pigments include various chromates such as yellow lead, zinc chromate, and molybdate orange; various ferrocyanic compounds such as Prussian blue; titanium oxide, zinc white, mapico yellow, iron oxide, red iron oxide, and chromium oxide.
  • various metal oxides such as green and zirconium oxide; various sulfides and selenides such as cadmium yellow, cadmium red, and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various types such as calcium silicate and ultramarine blue various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powders such as aluminum powder, gold powder, silver powder, copper powder, bronze powder and brass powder. pigments; flake pigments of these metals, mica flake pigments; metallic pigments and pearl pigments such as mica flake pigments coated with metal oxides and mica-like iron oxide pigments; graphite, carbon black and the like.
  • Extender pigments include, for example, precipitated barium sulfate, rice flour, precipitated calcium carbonate, calcium bicarbonate, Kansui stone, alumina white, silica, hydrous fine silica (white carbon), ultrafine anhydrous silica (Aerosil), silica sand (silica sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess, and the like.
  • plastic pigments include "Glandole PP-1000" and "PP-2000S” manufactured by DIC Corporation.
  • inorganic oxides such as titanium oxide and zinc oxide as white pigments, and carbon black as black pigments, since they are excellent in durability, weather resistance, and design.
  • the content of the pigment in the two-component curing adhesive of the present embodiment is 1 to 400 parts by mass with respect to 100 parts by mass of the total solid content of the polyisocyanate composition (X) and the polyol composition (Y). is preferred, and 10 to 300 parts by mass is more preferred.
  • the content of the pigment is 1 to 400 parts by mass, a two-part curing adhesive having excellent adhesion and anti-blocking properties can be obtained.
  • the two-component curing adhesive of the present invention may contain other additives in addition to the components described above, if necessary.
  • the additive may be contained in either one of the polyisocyanate composition (X) and the polyol composition (Y), or may be contained in both.
  • the additive may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) during coating of the two-component curing adhesive.
  • Additives include, for example, leveling agents; inorganic fine particles such as colloidal silica and alumina sol; polymethylmethacrylate-based organic fine particles; antifoaming agents; Deactivator; peroxide decomposer; flame retardant; reinforcing agent; plasticizer; lubricant; rust inhibitor; fluorescent whitening agent; is mentioned.
  • the two-component curable adhesive of the present embodiment is a two-component curable adhesive using a curing reaction between the polyisocyanate composition (X) and the polyol composition (Y), wherein the polyisocyanate composition (X) is It contains polyisocyanate (A), polyol composition (Y) contains polyol (B), and extensional viscosity of polyisocyanate composition (X) and polyol composition (Y) is 0.1 to 10 Pa ⁇ s.
  • the two-component curing adhesive of the present embodiment can be used in the case of producing a laminated film by a production method having a two-component separate application step, the polyisocyanate composition (X) applied on the first film, In the step of contacting the polyol composition (Y) coated on the second film, misting is less likely to occur, and the initial cohesion is also excellent.
  • the two-component curable adhesive of the present embodiment can be used, for example, when manufacturing a laminated film using a manufacturing method including a two-component mixed coating process and a manufacturing method including a two-component separate coating process. It can be suitably used for
  • the two-component curing adhesive of the present embodiment is 0.1 to 10 Pa s, thereby suppressing the occurrence of misting. can.
  • the initial cohesive force may be insufficient, but the extensional viscosity of the polyisocyanate composition (X) and the polyol composition (Y) is 0.1 to 10 Pa s. This makes it possible to solve the problem of initial cohesion. For this reason, the two-component curing adhesive of the present embodiment can be used particularly suitably when manufacturing a laminated film using a method having a two-component separate coating process.
  • the elongational viscosity of the polyisocyanate composition (X) and the polyol composition (Y) is 0.1 to 10 Pa ⁇ s.
  • the two-component curing adhesive of the present embodiment has good reactivity between the polyol composition (Y) and the polyisocyanate composition (X). Therefore, the aging temperature can be lowered and the aging time can be shortened.
  • FIG. 1 is a cross-sectional view showing an example of the laminated film according to this embodiment.
  • the laminated film 11a of this embodiment has an adhesive layer 10 between the first film W1 and the second film W2.
  • the adhesive layer 10 is made of the cured two-component curing adhesive of the above embodiment.
  • the film In the laminated film 11a of the present embodiment, it is preferable to use plastic films used for known laminated films for the films used as the first film W1 and the second film W2.
  • the first film W1 include base films such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") film, nylon (OPA) film, biaxially oriented polypropylene (OPP) film, various vapor deposition films, Aluminum foil or the like can be used.
  • PET polyethylene terephthalate
  • OPA nylon
  • OPP biaxially oriented polypropylene
  • various vapor deposition films Aluminum foil or the like
  • Aluminum foil or the like can be used.
  • a sealant film such as an unstretched polypropylene (CPP) film or a linear low density polyethylene (LLDPE) film can be used.
  • CPP unstretched polypropylene
  • LLDPE linear low density polyethylene
  • Paper such as natural paper, synthetic paper, and coated paper may be used as the first film W1 and the second film W2.
  • a printed layer may be provided on the outer surface or inner surface side of the first film W1 and/or the second film W2, if necessary.
  • the laminated film 11a of the present embodiment is industrially used as a flexible packaging film, a flexible packaging (package whose shape is formed by putting contents in it) material, a packaging material for filling detergents, medicines, foods, beverages, etc. can be used as intended.
  • Specific examples of detergents and chemicals include liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, and liquid conditioners. Foods and beverages are not particularly limited.
  • the laminated film 11a of this embodiment can be used as a package by forming it into a bag shape.
  • the laminated film 11a of the present embodiment has an adhesive layer 10 between the first film W1 and the second film W2, and the adhesive layer 10 is formed from the cured two-component curable adhesive of the above embodiment.
  • the laminated film 11a of the present embodiment can be manufactured using the two-component curable adhesive of the above embodiment, which has excellent initial cohesive strength and is less prone to misting even when the step of applying it onto the film is performed. . Therefore, the laminated film of the present embodiment can be efficiently manufactured using a manufacturing method such as a manufacturing method including a two-component mixed coating process and a manufacturing method including a two-component separate coating process.
  • the two-component curing adhesive of the above embodiment cures in a short time and/or at a low temperature, the laminated film 11a of this embodiment can be produced with a small amount of energy.
  • FIG. 2 is a front view of the laminated film manufacturing apparatus according to the present embodiment.
  • 3 is a front view showing a main part of a polyisocyanate coating section in the laminated film manufacturing apparatus shown in FIG. 2.
  • FIG. 4 is a front view showing a main part of a polyol coating section in the laminated film manufacturing apparatus shown in FIG. 2.
  • the laminated film manufacturing apparatus 1 shown in FIG. 2 uses the two-component curing adhesive of the present embodiment described above to separate the first film W1 unwound from the roll and the second film W2 unwound from the roll.
  • This apparatus forms the adhesive layer 10 between the first film W1 and the second film W2 by sticking them together, and manufactures the above-described laminated film 11a of the present embodiment wound into a roll.
  • the laminated film manufacturing apparatus 1 of the present embodiment includes a first unwinding section 11, a polyisocyanate coating section 12 (first coating section), a second unwinding section 13, A polyol coating unit 14 (second coating unit) and a bonding device 15 are provided.
  • the first unwinding section 11 delivers the first film W1 to the polyisocyanate coating section 12 .
  • the first film W1 is rotatably mounted on the film mounting portion 111 of the first unwinding portion 11 .
  • the polyisocyanate coating section 12 applies the polyisocyanate composition (X) of the two-component curing adhesive of the present embodiment to the first film W1 delivered from the first unwinding section 11 .
  • the polyisocyanate coating section 12 is a four-roll squeeze roll coater.
  • the polyisocyanate coating section 12 includes an application roll 121 , a doctor roll 122 , a metering roll 123 , a coating roll 124 and a backing roll 125 .
  • a liquid reservoir 120 is provided at a portion where the application roll 121 and the doctor roll 122 face each other.
  • the application roll 121 is a roll having an outer peripheral surface made of an elastic material such as rubber.
  • the doctor roll 122 is a roll having an outer peripheral surface made of metal (inelastic material). As shown in FIG. 3, the application roll 121 and the doctor roll 122 are rotatably supported by the polyisocyanate coating section 12 so that their rotation axes are parallel to each other. The outer peripheral surface of the application roll 121 and the outer peripheral surface of the doctor roll 122 face each other with a minute gap therebetween.
  • a pair of barrier plates 126 is installed at a predetermined interval in the direction of the rotation axis of the application roll 121 and the doctor roll 122 above the portion where the application roll 121 and the doctor roll 122 face each other.
  • a liquid reservoir 120 is formed by the pair of barrier plates 126 , the outer peripheral surface of the application roll 121 , and the outer peripheral surface of the doctor roll 122 .
  • the liquid reservoir 120 temporarily stores the polyisocyanate composition (X).
  • the polyisocyanate composition (X) is supplied to the liquid reservoir 120 from a polyisocyanate supply section (not shown). Thereby, the polyisocyanate composition (X) stored in the liquid reservoir 120 is held at a constant amount.
  • the doctor roll 122 preferably has a temperature control section (not shown).
  • the temperature control section keeps the polyisocyanate composition (X) stored in the liquid reservoir section 120 at a constant temperature and stabilizes the viscosity of the polyisocyanate composition (X). Thereby, the outer peripheral surface of the doctor roll 122 is kept at a constant temperature.
  • the application roll 121 and doctor roll 122 rotate downward in the liquid reservoir 120 .
  • the outer peripheral surface of the doctor roll 122 is coated with the polyisocyanate composition (X) that has passed through the minute gaps.
  • the polyisocyanate coating section 12 rotatably supports a metering roll 123, a coating roll 124, and a backing roll 125.
  • the polyisocyanate composition (X) applied to the outer peripheral surface of the doctor roll 122 is transferred to the metering roll 123 .
  • the rotating shaft of the metering roll 123 is arranged parallel to the rotating shaft of the doctor roll 122 .
  • the outer peripheral surface of the metering roll 123 is made of an elastic material such as rubber. The outer peripheral surface of the metering roll 123 is pressed against the outer peripheral surface of the doctor roll 122 .
  • the polyisocyanate composition (X) applied to the outer peripheral surface of the metering roll 123 is transferred to the coating roll 124 .
  • the rotation axis of the coating roll 124 is arranged parallel to the rotation axis of the metering roll 123 .
  • the outer peripheral surface of the coating roll 124 is formed of a metal material. The outer peripheral surface of the coating roll 124 is pressed against the outer peripheral surface of the metering roll 123 .
  • the backing roll 125 is arranged so that the rotating shafts of the coating roll 124 are parallel to each other.
  • the backing roll 125 sandwiches the second film W2 between itself and the coating roll 124, and conveys the second film W2.
  • the backing roll 125 assists the transfer of the polyisocyanate composition (X) applied to the outer peripheral surface of the coating roll 124 to the first film W1.
  • the outer peripheral surface of the backing roll 125 is made of an elastic material such as rubber.
  • the coating roll 124 preferably has a constant temperature of the outer peripheral surface by a temperature control unit (not shown). This stabilizes the viscosity of the polyisocyanate composition (X) applied to the first film W1.
  • misting occurs when the polyisocyanate composition (X) moves between rolls due to transfer. Locations where misting usually occurs include, for example, the area where the doctor roll 122 and the metering roll 123 are in pressure contact, the area where the metering roll 123 and the coating roll 124 are in pressure contact, and the coating roll 124 and the backing roll. The vicinity where 125 is press-contacted can be mentioned.
  • misting it is necessary to reduce the rotation speed of each roll and the transport speed of the first film W1 in order to suppress the occurrence of misting.
  • the conveying speed of the first film W1 is lowered, the production efficiency of the laminated film 11a is lowered.
  • misting can be suppressed by using a composition having a specific elongational viscosity as the polyisocyanate composition (X).
  • a composition having a specific elongational viscosity as the polyisocyanate composition (X).
  • the laminated film 11a having excellent properties can be efficiently produced.
  • the polyisocyanate composition (X) is applied using a roll coater as in this embodiment, there are many locations where misting may occur. Therefore, the effect of strictly controlling the elongational viscosity of the polyisocyanate composition (X) becomes more pronounced.
  • the second unwinding section 13 delivers the second film W2 to the polyol coating section 14 .
  • the second film W2 is rotatably mounted on the film mounting portion 131 of the second unwinding portion 13 .
  • the polyol coating section 14 applies the polyol composition (Y) of the two-component curing adhesive of the present embodiment to the second film W2 delivered from the second unwinding section 13 .
  • the polyol coating unit 14, as shown in FIG. 4, is a gravure coating machine (gravure coater) that applies the polyol composition (Y) by gravure printing.
  • the polyol coating section 14 includes a gravure roll 141 , a chamber 142 , an impression cylinder 143 , a coating liquid tank 144 , a pump 145 and a temperature controller 146 .
  • the gravure roll 141 is a metal roll rotatably supported by the polyol coating section 14 .
  • a plurality of recesses are formed on the surface of the gravure roll 141 by, for example, laser engraving. By changing the volume, opening ratio, depth, etc. of the recesses, the amount of the coating liquid applied to the surface of the gravure roll 141 can be adjusted.
  • the gravure pattern applied to the surface of the gravure roll 141 is not particularly limited, and may be, for example, a honeycomb pattern.
  • the chamber 142 is a container that stores the polyol composition (Y).
  • the chamber 142 is arranged on one radial side of the gravure roll 141 .
  • the chamber 142 has a storage part 142a that stores the polyol composition (Y).
  • the storage part 142a is open to the gravure roll 141 side. A part of the outer peripheral surface of the gravure roll 141 is immersed in the polyol composition (Y) stored in the storage part 142a.
  • the reservoir 142a is sealed by a doctor blade 142b, a seal plate 142c and a pair of side plates 142d.
  • the chamber 142 has a plate-like doctor blade 142b.
  • the doctor blade 142b protrudes toward the gravure roll 141 from the upper end of the opening of the reservoir 142a.
  • the material of the doctor blade 142b is not particularly limited, and may be metal or resin, for example, stainless steel.
  • the tip of the doctor blade 142 b is pressed against the outer peripheral surface of the gravure roll 141 .
  • the tip of the doctor blade 142b seals the downstream side of the reservoir 142a in the roll rotation direction.
  • the doctor blade 142b scrapes off excess polyol composition (Y) adhering to the outer peripheral surface of the gravure roll 141 by rotating the gravure roll 141 and weighs it.
  • the chamber 142 has a plate-like seal plate 142c.
  • the seal plate 142c is made of resin.
  • the seal plate 142c protrudes toward the gravure roll 141 from the lower end of the opening of the reservoir 142a.
  • the tip of the seal plate 142 c is pressed against the outer peripheral surface of the gravure roll 141 .
  • the tip of the seal plate 142c seals the upstream side of the reservoir 142a in the roll rotation direction.
  • the chamber 142 has a side plate 142d made of resin.
  • the side plates 142d are attached to both side surfaces of the chamber 142, that is, both ends of the gravure roll 141 in the rotation axis direction.
  • the side surface of the side plate 142 d on the side of the gravure roll 141 has an arc shape along the shape of the gravure roll 141 and is pressed against the gravure roll 141 .
  • the impression cylinder 143 holds the second film W2 between itself and the gravure roll 141, and conveys the second film W2.
  • the impression cylinder 143 presses the second film W2 against the gravure roll 141 to transfer the polyol composition (Y) applied to the outer peripheral surface of the gravure roll 141 to the second film W2.
  • misting occurs when the polyol composition (Y) moves between rolls due to transfer.
  • the misting of the polyol composition (Y) occurs in the vicinity of the pressure contact between the gravure roll 141 and the impression cylinder 143 . If misting occurs, it is necessary to reduce the rotation speed of each roll and the conveying speed of the second film W2 in order to suppress the occurrence of misting.
  • the conveying speed of the second film W2 is lowered, the production efficiency of the laminated film 11a is lowered.
  • the polyol composition (Y) by using a composition having a specific elongational viscosity as the polyol composition (Y), the occurrence of misting can be suppressed. As a result, the laminated film 11a having excellent properties can be efficiently manufactured.
  • the coating liquid tank 144 is a container that stores the polyol composition (Y). As shown in FIG. 4, the coating liquid tank 144 is connected via a pipe to a pump 145 for flowing the polyol composition (Y) into the chamber 142 . Also, the coating liquid tank 144 is connected to the chamber 142 via a pipe. As a result, the polyol composition (Y) overflowing from the reservoir 142 a of the chamber 142 is recovered in the coating liquid tank 144 .
  • the pump 145 is connected to the coating liquid tank 144 and the chamber 142 via piping.
  • the pump 145 supplies the polyol composition (Y) stored in the coating liquid tank 144 to the reservoir 142 a of the chamber 142 .
  • a sine pump for example, can be used as the pump 145 .
  • the temperature controller 146 adjusts the temperature of the polyol composition (Y) stored in the coating liquid tank 144. This keeps the temperature of the polyol composition (Y) constant and stabilizes the viscosity of the polyol composition (Y).
  • the temperature controller 146 is, for example, a water temperature controller that heats water, which is a heat medium, with a heater and circulates around the polyol composition (Y) stored in the coating liquid tank 144 .
  • the bonding device 15 includes a bonding section 151 and a winding section 152, as shown in FIG.
  • the bonding portion 151 is a surface coated with the polyisocyanate composition (X) in the first film W1 delivered from the polyisocyanate coating portion 12 and a polyol composition in the second film W2 delivered from the polyol coating portion 14.
  • the coated surface of (Y) is pasted together.
  • the winding section 152 winds up the laminated film 11 a bonded by the bonding section 151 .
  • the lamination section 151 has a pair of lamination rolls R1 and R2, as shown in FIG.
  • the lamination rolls R1 and R2 sandwich and bond the first film W1 and the second film W2, and convey them.
  • the two laminate rolls R1 and R2 are kept at a constant temperature on the outer peripheral surface by a temperature control unit (not shown). This stabilizes the curing of the two-component curing adhesive.
  • the lamination unit 151 passes the first film W1 and the second film W2 between two laminate rolls R1 and R2 arranged opposite to each other, and sends them out from the polyisocyanate coating unit 12.
  • the coated surface of the first film W1 fed from the first film W1 and the coated surface of the second film W2 delivered from the polyol coating unit 14 are brought into contact with each other and bonded together.
  • the polyisocyanate composition (X) applied to the first film W1 and the polyol composition (Y) applied to the second film W2 are mixed to form a two-component curing adhesive. Curing of the agent is started, and the first film W1 and the second film W2 are attached and fixed.
  • the winding section 152 winds up the laminated film 11a formed by bonding the first film W1 and the second film W2 together in the bonding section 151 .
  • the method for manufacturing the laminated film 11a of the present embodiment includes a two-liquid separate coating process and an adhesive layer forming process. In this embodiment, the two-liquid separate application step and the adhesive layer forming step are performed continuously.
  • the two-liquid separate application step includes a first application step of applying a polyisocyanate composition (X) containing a polyisocyanate (A) and having an elongational viscosity of 0.1 to 10 Pa s on the first film W1, and a polyol ( B) and a second coating step of coating the second film W2 with the polyol composition (Y) having an extensional viscosity of 0.1 to 10 Pa ⁇ s.
  • the first coating process and the second coating process are performed simultaneously.
  • first coating process A method of performing the first coating step using the laminated film manufacturing apparatus 1 shown in FIGS. 2 to 4 will be described.
  • the first film W1 is delivered from the first unwinding section 11 to the polyisocyanate coating section 12 .
  • each roll is rotated in the direction indicated by the arrow in FIG.
  • the polyisocyanate composition (X) stored in the liquid reservoir 120 is applied to the surface of the doctor roll 122 .
  • the temperature of the polyisocyanate composition (X) stored in the liquid reservoir 120 is preferably adjusted to 25° C. to 80° C., preferably 25° C. to 40° C., by a temperature control unit (not shown). is more preferable.
  • the shear viscosity of the polyisocyanate composition (X) at 40° C. is preferably 3000 mPa ⁇ s or less, more preferably 2000 mPa ⁇ s or less.
  • the polyisocyanate composition (X) applied to the doctor roll 122 is sequentially transferred to the metering roll 123 and the coating roll 124 .
  • Each roll of the polyisocyanate coating section 12 is set so that the rotational speed increases sequentially.
  • the coating thickness of the polyisocyanate composition (X) gradually decreases, and the coating roll 124 adjusts the coating thickness (coating amount) to a predetermined level.
  • the polyisocyanate composition (X) transferred to the coating roll 124 is transferred to the first film W ⁇ b>1 conveyed between the coating roll 124 and the backing roll 125 . Thereby, the polyisocyanate composition (X) is applied to the first film W1.
  • the coating amount of the polyisocyanate composition (X) applied to the first film W1 is preferably 0.5 to 3.0 g/m 2 , more preferably 0.5 to 2 .0 g/ m2 .
  • the first film W ⁇ b>1 coated with the polyisocyanate composition (X) is delivered to the bonding device 15 .
  • the second film W2 is delivered from the second unwinding section 13 to the polyol coating section .
  • the gravure roll 141 and impression cylinder 143 are rotated in the directions indicated by the arrows in FIG.
  • the surface of the gravure roll 141 is coated with the polyol composition (Y) in the chamber 142 on the second film W2.
  • the coating amount of the polyol composition (Y) applied to the second film W2 is preferably 0.5 to 3.0 g/m 2 , more preferably 0.5 to 2.0 g / m2 .
  • the temperature of the polyol composition (Y) stored in the coating liquid tank 144 is preferably adjusted to 25° C. to 80° C., preferably 25° C. to 40° C., by the temperature controller 146. is more preferable.
  • the viscosity of the polyol composition (Y) is set to a viscosity suitable for a gravure coating machine.
  • the rotation direction of the gravure roll 141 may be forward rotation, which is the same direction as the transport direction of the second film W2, or reverse rotation, which is the opposite direction to the transport direction of the second film W2.
  • the gravure roll 141 transfers the polyol composition (Y) to the second film W2 while rotating in the direction opposite to the conveying direction of the second film W2.
  • the appearance of the polyol composition (Y) applied to the second film W2 can be made good without vertical streaks, roll marks, and the like.
  • the second film W ⁇ b>2 coated with the polyol composition (Y) is delivered to the bonding device 15 .
  • Adhesive layer forming step In the adhesive layer forming step, by laminating the first film W1 and the second film W2, the polyisocyanate composition (X) applied on the first film W1 and the polyol applied on the second film It is brought into contact with the composition (Y) to cause a curing reaction.
  • the first film W1 and the second film W2 are sandwiched between two lamination rolls R1 and R2 facing each other while being in contact with each other. pass between two laminate rolls R1, R2. Then, the first film W1 and the second film W2 are laminated together by the pressure from the two lamination rolls R1 and R2.
  • the temperature of the outer peripheral surfaces of the two laminate rolls R1 and R2 is preferably 40°C to 80°C, more preferably 40°C to 60°C.
  • the pressure from the two laminating rolls R1, R2 to the first film W1 and the second film W2 can be, for example, 3-300 kg/cm 2 .
  • the coated surface of the first film W1 delivered from the polyisocyanate coating unit 12 and the second film delivered from the polyol coating unit 14 are sandwiched between the two lamination rolls R1 and R2.
  • the coated surface of W2 contacts.
  • the polyisocyanate composition (X) applied to the first film W1 and the polyol composition (Y) applied to the second film W2 are mixed, and curing of the two-component curable adhesive is started. be.
  • the laminated film 11a having the adhesive layer 10 between the first film W1 and the second film W2 is obtained.
  • the laminated film 11a produced by bonding the first film W1 and the second film W2 together in the bonding section 151 is conveyed to the winding section 152 .
  • the laminated film 11 a conveyed to the winding section 152 is wound by the winding section 152 .
  • the film transport speed (the winding speed of the laminated film 11a in the winding unit 152) when manufacturing the laminated film 11a can be set to, for example, 30 to 300 m/min. preferably 100 to 250 m/min.
  • misting with the polyisocyanate composition (X) and the polyol composition (Y) can suppress the occurrence of Therefore, even if the film conveying speed is 30 m/min or more, the workability is not deteriorated due to the misting of the two-component curing adhesive.
  • the laminated film can be efficiently produced continuously at a high film transport speed of 30 m/min or more. If the film conveying speed exceeds 300 m/min, coating problems other than misting, problems during the transfer itself, problems during lamination, and the like may occur. Therefore, it is preferable to set the film transport speed to 300 m/min or less.
  • the laminated film 11a obtained by the manufacturing method of the present embodiment is obtained by bonding the first film W1 and the second film W2 together in the bonding section 151, and after being wound up by the winding section 152, is allowed to stand at room temperature as necessary.
  • aging is performed by storing for 3 to 48 hours under heating. By performing aging, the two-component curing adhesive is sufficiently cured, and practical physical properties as the adhesive layer 10 may be exhibited.
  • the aging time can be shortened because the polyisocyanate composition (X) and the polyol composition (Y) use a two-component curing adhesive having a specific elongational viscosity and excellent initial cohesive strength.
  • the manufacturing method of the present embodiment has a wide selection of manufacturing processes, and can improve work efficiency.
  • the manufacturing apparatus 1 of the laminated film 11a of the present embodiment includes a polyisocyanate coating unit 12 that applies a polyisocyanate composition (X) having an elongational viscosity of 0.1 to 10 Pa s to the first film W1, and an elongational viscosity A polyol coating portion 14 for applying a polyol composition (Y) having a value of 0.1 to 10 Pa s on the second film W2, a polyisocyanate composition (X) coated surface of the first film W1, and a second and a laminating device 15 for laminating the film W2 with the surface coated with the polyol composition (Y). Therefore, the manufacturing apparatus 1 of the laminated film 11a of the present embodiment uses the liquid-curable adhesive of the present embodiment and manufactures the laminated film 11a by the manufacturing method of the present embodiment having a two-liquid separate application process. can be preferably used.
  • the polyisocyanate coating unit 12 applies the polyisocyanate composition (X) having an extensional viscosity of 0.1 to 10 Pa s to the first film W1. and the polyol coating section 14 applies the polyol composition (Y) having an extensional viscosity of 0.1 to 10 Pa ⁇ s to the second film W2. Therefore, in the manufacturing apparatus 1 of the laminated film 11a of the present embodiment, the polyisocyanate composition (X)-coated surface of the first film W1 and the polyol composition (Y)-coated surface of the second film W2 are attached. Misting of the two-component curable adhesive is less likely to occur in the pasting device. Therefore, by using the manufacturing apparatus 1 for the laminated film 11a of the present embodiment, the laminated film 11a can be efficiently produced at a continuously high film transport speed.
  • the polyol coating section 14 may be equipped with a gravure coater with a wide range of selection such as the viscosity of the polyol composition (Y), or a roll coater with which misting of the polyol composition (Y) is likely to occur. may be provided, and the options for the coating device for the polyol composition (Y) in the polyol coating section 14 can be increased.
  • the viscosity of the polyol composition (Y) is low and problems such as dripping may occur with a roll coater. However, dripping does not occur, and coating quality can be improved to manufacture a high-quality laminated film 11a. Moreover, by using a gravure coater, the configuration of the polyol coating section 14 can be simplified, and the manufacturing apparatus for the laminated film 11a can be miniaturized.
  • a roll coater is used in the polyisocyanate coating section 12 that applies the relatively high viscosity polyisocyanate composition (X) to the first film W1.
  • a roll coater it is possible to apply even when the viscosity of the polyisocyanate composition (X) is relatively high, and the range of selection of the material of the polyisocyanate composition (X) is widened.
  • the method for producing the laminated film 11a of the present embodiment comprises a first coating step of applying the polyisocyanate composition (X) having an elongational viscosity of 0.1 to 10 Pa ⁇ s to the first film W1, and By laminating the first film W1 and the second film W2, and a two-liquid separate coating step consisting of a second coating step of applying the polyol composition (Y) of 1 to 10 Pa s to the second film W2. and an adhesive layer forming step of contacting the polyisocyanate composition (X) applied on the first film W1 and the polyol composition (Y) applied on the second film W2 to cause a curing reaction. .
  • the step of mixing the polyisocyanate composition (X) and the polyol composition (Y) is not required. Therefore, the workability is excellent as compared with the case of having a step of mixing the polyisocyanate composition (X) and the polyol composition (Y).
  • the polyisocyanate composition (X) and the polyol composition (Y) are not mixed, there is no limitation due to the pot life of the two-component curing adhesive, and the two-component curing adhesive of the present embodiment, which cures quickly. drug can be used.
  • the polyisocyanate composition (X) having an elongational viscosity of 0.1 to 10 Pa s is applied to the first film
  • a polyol composition (Y) having an elongational viscosity of 0.1 to 10 Pa ⁇ s is applied to the second film W2. Therefore, in the method for producing the laminated film 11a of the present embodiment, the polyisocyanate composition (X) applied on the first film and the polyol composition (Y) applied on the second film are brought into contact.
  • misting of the two-component curing adhesive is less likely to occur, and the laminated film can be efficiently produced at a continuously high film transport speed.
  • a roll coater is used as the polyisocyanate-coated portion 12, but when the viscosity of the polyisocyanate composition (X) is low, etc., a gravure coater may be used as the polyisocyanate-coated portion 12. . Further, in the above-described embodiment, a gravure coater is used as the polyol-coated portion 14, but a roll coater may be used as the polyol-coated portion 14 when the polyol composition (Y) can be applied. .
  • the temperature of the polyol composition (Y) stored in the coating liquid tank 144 is adjusted by the temperature controller 146. Furthermore, the temperature of the polyol composition (Y) stored in the storage section 142a of the chamber 142 and/or the temperature of the gravure roll 141 may be adjusted. Thereby, the viscosity of the polyol composition (Y) during coating can be further stabilized, and the coating quality and the quality of the laminated film 11a can be further improved.
  • the polyol coating section 14 that applies the polyol composition (Y) to the second film W2 and the An example of manufacturing the laminated film 11a by a production method having a two-liquid separate application process using the laminated film 11a production apparatus 1 having the laminating device 15 for laminating the first film W1 and the second film W2.
  • the laminated film 11a may be manufactured by a manufacturing method having a two-liquid mixing coating process using the manufacturing apparatus shown below, for example.
  • FIG. 5 is a front view for explaining another example of the manufacturing apparatus used for manufacturing the laminated film of this embodiment.
  • a laminated film manufacturing apparatus 1A shown in FIG. the apparatus forms the adhesive layer 10 between the first film W1 and the second film W2, and manufactures the laminated film 11a of the present embodiment, which is wound into a roll.
  • the laminated film manufacturing apparatus 1A shown in FIG. 5 includes, as shown in FIG. . 5 differs from the laminated film manufacturing apparatus 1 shown in FIG. 2 in that a mixture coating section 12A is provided instead of the polyisocyanate coating section 12; It is only the portion without the polyol coating section 14 in the laminated film manufacturing apparatus 1 shown in FIG. In the laminated film manufacturing apparatus 1A shown in FIG. 5, the same members as those in the laminated film manufacturing apparatus 1 shown in FIG.
  • the laminated film manufacturing apparatus 1A shown in FIG. 5 is provided with a mixing device (not shown) for mixing the polyisocyanate composition (X) and the polyol composition (Y) of the two-component curing adhesive. Further, in the laminated film manufacturing apparatus 1A shown in FIG. 5, instead of the polyisocyanate supplying section of the laminated film manufacturing apparatus 1 shown in FIG. is provided.
  • the following manufacturing method can be used.
  • the first film W1 is delivered from the first unwinding section 11 to the mixed liquid coating section 12A.
  • each roll is rotated in the direction indicated by the arrow in FIG.
  • the mixed liquid of the polyisocyanate composition (X) and the polyol composition (Y) stored in the liquid reservoir 120 is applied to the surface of the doctor roll 122 .
  • the temperature of the mixed liquid stored in the liquid reservoir 120 is preferably adjusted to 25° C. to 80° C., more preferably 25° C. to 40° C., by a temperature control unit (not shown). .
  • the shear viscosity of the mixture at 40° C. is preferably 2000 mPa ⁇ s or less, more preferably 1800 mPa ⁇ s or less.
  • the polyol composition (Y) and the polyisocyanate composition (X) are mixed in the mixing device to initiate curing of the two-component curing adhesive.
  • the mixed liquid applied to the doctor roll 122 is sequentially transferred to the metering roll 123 and the coating roll 124 .
  • the mixed liquid transferred to the coating roll 124 is transferred to the first film W ⁇ b>1 conveyed between the coating roll 124 and the backing roll 125 .
  • the mixed liquid is applied to the first film W1.
  • the coating amount of the mixture applied to the first film W1 is preferably 0.5 to 3.0 g/m 2 , more preferably 0.5 to 2.0 g/m 2 . is.
  • the first film W1 coated with the mixed liquid in the mixed liquid coating section 12A is delivered to the bonding device 15 as shown in FIG.
  • the laminating unit 151 of the laminating device 15 As shown in FIG. 5, two laminates are arranged facing each other in a state where the surface of the first film W1 coated with the liquid mixture is in contact with the second film W2. It is sandwiched between rolls R1 and R2 and passes between the two laminating rolls R1 and R2. Then, the first film W1 and the second film W2 are laminated together by the pressure from the two lamination rolls R1 and R2.
  • the temperature of the outer peripheral surfaces of the two laminate rolls R1 and R2 is preferably 40°C to 80°C, more preferably 40°C to 60°C.
  • the pressure from the two laminating rolls R1, R2 to the first film W1 and the second film W2 can be, for example, 3-300 kg/cm 2 .
  • the laminated film 11a having the adhesive layer 10 between the first film W1 and the second film W2 is obtained.
  • the laminated film 11a produced by bonding the first film W1 and the second film W2 together in the bonding section 151 is conveyed to the winding section 152 .
  • the laminated film 11 a conveyed to the winding section 152 is wound by the winding section 152 .
  • the film transport speed (the winding speed of the laminated film 11a in the winding unit 152) when manufacturing the laminated film 11a can be set to, for example, 30 to 300 m/min. preferably 100 to 250 m/min.
  • the laminated film 11a is produced using the two-component curing adhesive of the present embodiment, misting by the mixed liquid which is the component containing the polyol composition (Y) can be suppressed. Therefore, even if the film transport speed is 30 m/min or more, the misting of the mixed solution does not lower the workability.
  • the laminated film can be efficiently produced continuously at a high film transport speed of 30 m/min or more. If the film conveying speed exceeds 300 m/min, coating problems other than misting, problems during the transfer itself, problems during lamination, and the like may occur. Therefore, it is preferable to set the film transport speed to 300 m/min or less.
  • the laminated film 11a of the present embodiment is manufactured using the two-component curing adhesive of the present embodiment, the mixed liquid, which is a component containing the polyol composition (Y), is applied onto the second film W2.
  • misting due to the polyol composition (Y) is less likely to occur. Therefore, the laminated film 11a of the present embodiment can be efficiently manufactured using a manufacturing method having a two-liquid mixing coating process.
  • the laminated film 11a is formed by using a manufacturing method having a two-component separate coating process including a step of coating only the polyol composition (Y) on the film as the manufacturing method having the two-component separate coating process.
  • a manufacturing method having a two-component separate coating process including a step of coating only the polyol composition (Y) on the film as the manufacturing method having the two-component separate coating process.
  • a mixed solution of the polyisocyanate composition and the polyol composition is applied onto the first film
  • a solution containing a curing accelerator is applied onto the second film.
  • a mixture of a part of the polyol composition and the polyisocyanate composition is applied on the first film
  • the remainder of the polyol composition and the curing accelerator are applied.
  • the solution containing is applied to the second film.
  • Polyisocyanate composition (X-1) [Production of polyisocyanate (A)] 41.9 parts of 4,4-diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") and 13.0 parts of 2,4'-MDI were added to a flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube. and 0.1 part of xylylene diisocyanate were placed in a reaction vessel, stirred under nitrogen gas, and heated to 60°C.
  • MDI 4,4-diphenylmethane diisocyanate
  • a polyisocyanate composition (X-1) composed of the polyisocyanate (A) was obtained by adding dropwise in batches and stirring at 80° C. for 5 to 6 hours to cause a urethanization reaction.
  • the isocyanate content of polyisocyanate (A) was measured by a titration method using di-n-butylamine. As a result, it was 14% by mass. Moreover, the melt shear viscosity at 40° C. was measured for the polyisocyanate (A). As a result, it was 1500 mPa ⁇ s.
  • Polyisocyanate composition (X-2, X-3) As the polyisocyanate compositions X-2 and X-3, the following were prepared. X-2: 2K-SF-220A (manufactured by DIC Corporation), isocyanate content (14% by mass) X-3: 2K-SF-700A (manufactured by DIC Corporation), isocyanate content (21% by mass)
  • Polyol Compositions (Y-1) to (Y-6) The polyol (B), polyamine (C) and additives shown in Table 1 were mixed in the proportions shown in Table 1 to obtain polyol compositions (Y-1) to (Y-6).
  • EC310 Polyoxypropylene polyamine (manufactured by BASF) Baxxdur EC310 "catalyst” ⁇ -caprolactam: 2-oxohexamethyleneimine (manufactured by Kanto Chemical Co., Ltd.) ⁇ -valerolactam: tetrahydro-2H-pyran-2-one (manufactured by Kanto Chemical Co., Ltd.) DBTDL: Dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.) Neostan U-100 Bi-Zn: mixed catalyst of bismuth neodecanoate and zinc neodecanoate (manufactured by The Shepherd Chemical Company) Bicat 8108/Z mixture "adhesion promoter" OFS-6040: 3-glycidyloxypropyltrimethoxysilane (manufactured by Dow Corning Toray Co., Ltd.) KBM903:
  • the hydroxyl value or amine value of the materials used in the polyol compositions (Y-1) to (Y-8) was determined by the method shown below.
  • the hydroxyl value was obtained according to the hydroxyl value measurement method of JIS-K0070.
  • the amine value was determined according to ASTM D2073 Amine Value Standard Test Method. Then, the sum of the hydroxyl value and the amine value contained in the polyol compositions (Y-1) to (Y-8) was determined. The results are shown in Tables 1 and 2.
  • the elongational viscosity at an elongation speed of 4000 s -1 was measured by the method shown below. .
  • Table 2 shows the results.
  • the elongational viscosity was measured according to the capillary rheometer evaluation method described in JIS-7199 (ISO 11443, ASTM D 3835).
  • a capillary die with a length of 10 mm and a diameter of 0.5 mm and a capillary die with a length of 0.25 mm and a diameter of 0.5 mm were used.
  • a temperature of 40° C. and a shear rate of 1000-300000 s ⁇ 1 the pressure drop was removed using the Bergley correction to obtain the true shear viscosity.
  • the elongation velocity and the corresponding elongation viscosity were determined using the Cogswell equation.
  • Examples 1 to 7, Comparative Examples 1 to 3 Polyisocyanate compositions (X-1) to (X-3) and polyol compositions (Y-1) to (Y-8) were used in the proportions shown in Table 2, and the 2 to 4, laminated films of Examples 1 to 7 and Comparative Examples 1 to 3 were produced at film transport speeds of 100, 150, 200 and 250 m/min, respectively.
  • the ratios of the polyisocyanate compositions (X-1) to (X-3) and the polyol compositions (Y-1) to (Y-8) are the polyisocyanate compositions (X-1) to
  • the molar ratio of the isocyanate group of (X-3) to the sum of the hydroxyl value and amine value of the polyol compositions (Y-1) to (Y-8) [isocyanate group/(hydroxyl value + amine value) ] is in the range of 1.4 to 1.6.
  • the molar ratio is described as the NCO excess.
  • the functional group content of the polyisocyanate composition shown in Table 2 is the isocyanate content (%) of the polyisocyanate compositions (X-1) to (X-3).
  • the functional group content of the polyol composition described in Table 2 is the sum of the hydroxyl value and amine value of the polyol composition (mgKOH/g).
  • One of the polyisocyanate compositions (X-1) to (X-3) was applied to the corona-treated surface of a 12 ⁇ m-thick single-sided corona-treated PET film (first film) with a roll coater (first coating process).
  • first coating process the temperature of the polyisocyanate composition (X) stored in the coating liquid tank was set to 40°C.
  • any one of the polyol compositions (Y-1) to (Y-8) was applied to the aluminum-deposited surface of a 25 ⁇ m-thick aluminum-deposited polypropylene (VMCPP) film (second film) with a gravure coater. applied (second application step).
  • the total coating amount of the polyisocyanate compositions (X-1) to (X-3) and the polyol compositions (Y-1) to (Y-8) is 2. 0 g/m 2 .
  • the first coated portion and the second coated portion during coating were visually observed, and the misting properties were evaluated according to the criteria described later.
  • the adhesive layer forming process was performed continuously from the first coating process and the second coating process.
  • the adhesive layer forming step by laminating the first film and the second film, any of the polyisocyanate compositions (X-1) to (X-3) applied on the first film and the second It was carried out by contacting any one of the polyol compositions (Y-1) to (Y-8) coated on the film to cause a curing reaction.
  • the misting property in the process was evaluated, and 3 or more was regarded as acceptable.
  • Table 2 shows the results. (Evaluation of misting property) 4: No misting occurs in both the first and second coating parts 3: Some misting occurs in both the first and second coating parts 2: First coating part 1: Severe misting occurs in both the first and second coating parts
  • the laminate film was cut into strips having a width of 10 mm and a length of 200 mm, and only the first film was cut in the width direction from the first film side surface. Then, only the second film was cut in the width direction from the second film side of the laminated film at a position spaced 10 mm in the length direction in plan view from the cutting position of the first film. This gave a test piece having an adhesive layer with a plane area of 10 mm 2 between the cutting position of the first film and the cutting position of the second film.
  • One end of the obtained test piece in the length direction is held by a clamp, and the other end is pulled in the length direction at a speed of 5 mm / min using a tensile tester (Autograph AGS-J, manufactured by Shimadzu Corporation), The shear strength was measured.
  • Comparative Example 1 in which the polyisocyanate composition (X) had an elongational viscosity of more than 10 Pa s
  • Comparative Example 2 in which the polyol composition (Y) had an elongational viscosity of more than 10 Pa s
  • the film transport speed was 100 m/ Even at min, some misting occurred.
  • Comparative Example 3 in which the polyisocyanate composition (X) and the polyol composition (Y) had extensional viscosities of more than 10 Pa ⁇ s, misting occurred even when the film transport speed was 100 m/min.
  • Comparative Example 1 the shear strength was less than 1 N/10 mm even after 24 hours had passed since the end of the adhesive layer forming process. Moreover, in Comparative Example 2, the shear strength was less than 10 N/10 mm even after 12 hours had passed since the end of the adhesive layer forming step. Moreover, in Comparative Example 3, the shear strength was less than 5 N/10 mm even after 24 hours had passed since the end of the adhesive layer forming step. From this, it was confirmed that in Comparative Examples 1 to 3, the shear strength did not increase at an early stage, and the initial cohesive strength was inferior to that in Examples 1 to 7.
  • the laminated film obtained using the two-component curing adhesive of the present invention has excellent initial cohesive strength, is less prone to misting during its production, and has excellent properties. It can be manufactured efficiently.
  • 1 laminated film manufacturing apparatus, 10: adhesive layer, 11: first unwinding section, 11a: laminated film, 12: polyisocyanate coating section (first coating section), 13: second unwinding section, 14: Polyol coating part (second coating part), 15: Bonding device, 111: Film mounting part, 120: Liquid reservoir part, 121: Application roll, 122: Doctor roll, 123: Metering roll, 124: Coating roll, 125: backing roll, 126: barrier plate, 131: film mounting part, 141: gravure roll, 142: chamber, 142a: storage part, 142b: doctor blade, 142c: seal plate, 142d: side plate, 143: Impression cylinder, 144: Coating liquid tank, 145: Pump, 146: Temperature controller, 151: Bonding unit, 152: Winding unit, R1, R2: Lamination roll, W1: First film, W2: Second film .

Abstract

Provided is a two-component curing adhesive using a curing reaction of a polyisocyanate composition (X) and a polyol composition (Y), wherein the polyisocyanate composition (X) contains a polyisocyanate (A) and the polyol composition (Y) contains polyol (B). The extensional viscosity of the polyisocyanate composition (X) and of the polyol composition (Y) is from 0.1 to 10 Pa.s.

Description

二液硬化型接着剤、積層フィルム、積層フィルム製造装置、積層フィルムの製造方法Two-component curing adhesive, laminated film, laminated film manufacturing apparatus, laminated film manufacturing method
　本発明は、二液硬化型接着剤、積層フィルム、積層フィルム製造装置、積層フィルムの製造方法に関する。 The present invention relates to a two-component curing adhesive, a laminated film, a laminated film manufacturing apparatus, and a laminated film manufacturing method.
　従来、２枚のフィルムを接着剤で貼り合わせてなる積層フィルムには、接着剤として、ポリイソシアネート組成物とポリオール組成物との硬化反応を用いる二液硬化型接着剤を用いたものがある。
　二液硬化型接着剤を用いて積層フィルムを製造する方法として、古くから用いられている二液混合塗布工程を有する方法と、近年注目されている二液分別塗布工程を有する方法とがある。 Conventionally, there is a laminate film in which two films are bonded together using an adhesive, and a two-component curing adhesive that uses a curing reaction between a polyisocyanate composition and a polyol composition is used as the adhesive.
As a method for producing a laminated film using a two-component curing adhesive, there are a method having a two-component mixed coating process that has been used for a long time and a method having a two-component separate coating process that has been attracting attention in recent years.
　二液混合塗布工程を有する方法では、ポリイソシアネート組成物とポリオール組成物とを混合して混合液とし、これをフィルム上に塗布する二液混合塗布工程と、フィルム上に形成された塗膜上に別のフィルムを貼り合わせて硬化させる接着剤層形成工程とを有する方法が用いられている。 In the method having a two-liquid mixing coating step, the polyisocyanate composition and the polyol composition are mixed to form a mixed liquid, and the two-liquid mixing coating step of applying this on the film, and the coating film formed on the film. and a step of forming an adhesive layer in which another film is laminated and cured.
　二液分別塗布工程を有する方法としては、ポリイソシアネート組成物を第一フィルム上に塗布する第一塗布工程と、ポリオール組成物を第二フィルムに塗布する第二塗布工程とからなる二液分別塗布工程と、第一フィルムと第二フィルムとを積層することにより、第一フィルム上に塗布されたポリイソシアネート組成物と、第二フィルム上に塗布されたポリオール組成物とを接触させて硬化反応させる接着剤層形成工程とを有する方法がある。 As a method having a two-component separate coating step, a two-component separated coating comprising a first coating step of coating the polyisocyanate composition on the first film and a second coating step of coating the polyol composition on the second film. By laminating the first film and the second film, the polyisocyanate composition coated on the first film and the polyol composition coated on the second film are brought into contact and cured. There is a method having an adhesive layer forming step.
　近年、環境負荷の低減および作業環境の改善の観点から、有機溶剤を使用しない無溶剤型の二液硬化型接着剤の需要が高まっている。
　例えば、特許文献１～特許文献３には、一方の被着体に塗布された常温で液状の無溶剤型Ａ剤と他方の被着体に塗布された常温で液状の無溶剤型Ｂ剤とが接触した時に硬化反応を開始する二液分別塗布型接着剤が記載されている。 In recent years, from the viewpoint of reducing the environmental load and improving the working environment, the demand for solvent-free two-component curing adhesives that do not use organic solvents is increasing.
For example, Patent Documents 1 to 3 disclose solvent-free agent A that is liquid at room temperature applied to one adherend and solvent-free agent B that is liquid at room temperature and applied to the other adherend. A two-part split-coat adhesive is described that initiates a curing reaction when it comes into contact with the adhesive.
　特許文献１には、上記Ａ剤は、分子両末端にイソシアネート基を有する化合物を主成分としてなり、上記Ｂ剤は、分子両末端にアミノ基を有する化合物、分子内に３級アミンを有する化合物および粘着性付与樹脂を含有してなる二液分別塗布型ウレタン系接着剤が記載されている。
　特許文献２には、上記Ａ剤は、分子両末端にイソシアネート基を有する化合物を主成分としてなり、上記Ｂ剤は、分子両末端にアミノ基を有する化合物を主成分としてなる二液分別塗布型ウレタン系接着剤が記載されている。
　特許文献３には、上記Ａ剤は、分子両末端にイソシアネート基を有する化合物を主成分としてなり、上記Ｂ剤は、分子内に水酸基を有する化合物を主成分とする二液分別塗布型ウレタン系接着剤が記載されている。 In Patent Document 1, the above agent A is mainly composed of a compound having an isocyanate group at both ends of the molecule, and the above agent B is a compound having an amino group at both ends of the molecule and a compound having a tertiary amine in the molecule. and a tackifying resin are described.
In Patent Document 2, the A agent is mainly composed of a compound having an isocyanate group at both molecular ends, and the B agent is a two-component separate application type mainly composed of a compound having an amino group at both molecular ends. A urethane adhesive is described.
In Patent Document 3, the A agent is mainly composed of a compound having an isocyanate group at both ends of the molecule, and the B agent is a two-liquid separate application type urethane system mainly composed of a compound having a hydroxyl group in the molecule. Adhesives are mentioned.
特表２００３－１７１６４１号公報Japanese Patent Publication No. 2003-171641 特表２００３－１７１６４２号公報Japanese Patent Publication No. 2003-171642 特表２００３－１７１６４３号公報Japanese translation of PCT publication No. 2003-171643
　しかしながら、ポリイソシアネート組成物とポリオール組成物との硬化反応を用いる二液硬化型接着剤を用いて積層フィルムを製造する場合、接着直後の凝集力（初期凝集力）が不足する場合があった。その場合、十分な凝集力が得られるまでに時間を要することから、エージング工程の時間が長くなったり、４０～６０℃程度での加温が必要となったりすることがある。このため、積層フィルムの生産効率が低下するおそれがあった。特に、二液分別塗布工程を有する方法の多くでは、ポリイソシアネート組成物とポリオール組成物とが各々塗布された後に基材の間で初めて接触する。このことから、組成物の混合や組成物中の官能基間の反応が緩やかに起こり、初期凝集力の不足が問題となることが多かった。 However, when producing a laminated film using a two-component curing adhesive that uses a curing reaction between a polyisocyanate composition and a polyol composition, the cohesive force (initial cohesive force) immediately after adhesion may be insufficient. In this case, since it takes time to obtain sufficient cohesive strength, the aging process may take a long time, or heating at about 40 to 60° C. may be required. For this reason, there was a possibility that the production efficiency of the laminated film would be lowered. In particular, in many of the methods having a two-part separate coating process, contact between the substrates occurs for the first time after the polyisocyanate composition and the polyol composition are each coated. For this reason, mixing of the composition and reaction between functional groups in the composition occur slowly, often resulting in insufficient initial cohesive strength.
　また、二液硬化型接着剤を用いて積層フィルムを製造する場合、ミスティング（糸引き現象）が発生しやすいという不都合があった。ミスティングが発生すると、製造装置や設備に接着剤が飛散・付着することから、定期的な操業停止及び清掃等が必要となる。一方で、ミスティングの発生を低減するために、ロールの回転速度やフィルムの搬送速度を低下させると、生産効率が低下する。特に、二液分別塗布工程を有する方法を用いて、連続的に積層フィルムを製造する場合、フィルムの搬送速度を早くすると、二液硬化型接着剤のミスティングが発生しやすく、問題となっていた。 In addition, when manufacturing a laminated film using a two-component curing adhesive, there is the inconvenience that misting (stringing phenomenon) is likely to occur. When misting occurs, the adhesive scatters and adheres to manufacturing equipment and facilities, requiring periodic shutdown and cleaning. On the other hand, if the rotation speed of the rolls and the transport speed of the film are lowered in order to reduce the occurrence of misting, the production efficiency is lowered. In particular, when a laminated film is continuously produced by a method having a two-component separate coating process, misting of the two-component curable adhesive tends to occur when the film transport speed is increased, which poses a problem. rice field.
　本発明は、上記事情を鑑みてなされたものであり、ポリイソシアネート組成物とポリオール組成物との硬化反応を用いる二液硬化型接着剤であって、初期凝集力に優れ、且つ、フィルム上に塗布する工程を行ってもミスティングが発生しにくい二液硬化型接着剤を提供することを目的とする。
　本発明は、ポリイソシアネート組成物とポリオール組成物との硬化反応を用いる二液硬化型接着剤であって、フィルム上に塗布する工程を行ってもミスティングが発生しにくく、初期凝集力に優れる二液硬化型接着剤を使用して、効率よく製造でき、優れた特性を有する積層フィルムを提供することを目的とする。 The present invention has been made in view of the above circumstances, and is a two-component curing adhesive that uses a curing reaction between a polyisocyanate composition and a polyol composition, has excellent initial cohesive strength, and To provide a two-liquid curable adhesive that hardly causes misting even in a coating step.
The present invention is a two-component curable adhesive that uses a curing reaction between a polyisocyanate composition and a polyol composition, which hardly generates misting even when the step of coating on a film is performed, and has excellent initial cohesive strength. An object of the present invention is to provide a laminated film which can be produced efficiently by using a two-component curing adhesive and which has excellent properties.
　本発明は、ポリイソシアネート組成物とポリオール組成物との硬化反応を用いる、ミスティングが発生しにくく初期凝集力に優れる二液硬化型接着剤を使用して、二液分別塗布工程を有する製造方法により積層フィルムを製造する場合に、好適に使用できる積層フィルム製造装置を提供することを目的とする。
　本発明は、ポリイソシアネート組成物とポリオール組成物との硬化反応を用いる、ミスティングが発生しにくく初期凝集力に優れる二液硬化型接着剤を使用して、効率よく積層フィルムを製造できる積層フィルムの製造方法を提供することを目的とする。 The present invention uses a two-component curable adhesive that is resistant to misting and has excellent initial cohesive strength, using a curing reaction between a polyisocyanate composition and a polyol composition, and a production method having a two-component separate application step. An object of the present invention is to provide a laminated film manufacturing apparatus that can be suitably used when manufacturing a laminated film by a method.
The present invention uses a two-component curing adhesive that is resistant to misting and has excellent initial cohesive strength, using a curing reaction between a polyisocyanate composition and a polyol composition, to efficiently produce a laminated film. It aims at providing the manufacturing method of.
　本発明者は、上記課題を解決するために、ポリイソシアネート組成物とポリオール組成物との硬化反応を用いる二液硬化型接着剤を使用する際に、フィルム上に塗布する工程において発生するミスティングの発生を抑制し、且つ、接着剤の初期凝集力を高めるべく、鋭意検討を重ねた。
　その結果、ポリイソシアネート組成物およびポリオール組成物として、伸長粘度が０．１～１０Ｐａ・ｓであるものを用いることにより、初期凝集力が向上し、ミスティングの発生を抑制できることを見出し、本発明を想到した。
　すなわち、本発明は以下の事項に関する。 In order to solve the above problems, the present inventors have found that when using a two-component curing adhesive that uses a curing reaction between a polyisocyanate composition and a polyol composition, the misting that occurs in the process of applying it to the film In order to suppress the occurrence of this, and to increase the initial cohesive strength of the adhesive, we have made extensive studies.
As a result, it was found that by using a polyisocyanate composition and a polyol composition having an elongational viscosity of 0.1 to 10 Pa s, the initial cohesive force can be improved and the occurrence of misting can be suppressed. I came up with
That is, the present invention relates to the following matters.
［１］ポリイソシアネート組成物（Ｘ）とポリオール組成物（Ｙ）との硬化反応を用いる二液硬化型接着剤であって、
　前記ポリイソシアネート組成物（Ｘ）がポリイソシアネート（Ａ）を含み、
　前記ポリオール組成物（Ｙ）がポリオール（Ｂ）を含み、
　前記ポリイソシアネート組成物（Ｘ）および前記ポリオール組成物（Ｙ）の伸長粘度が０．１～１０Ｐａ・ｓである、二液硬化型接着剤。 [1] A two-component curing adhesive using a curing reaction between a polyisocyanate composition (X) and a polyol composition (Y),
The polyisocyanate composition (X) contains a polyisocyanate (A),
The polyol composition (Y) contains a polyol (B),
A two-component curing adhesive, wherein the polyisocyanate composition (X) and the polyol composition (Y) have extensional viscosities of 0.1 to 10 Pa·s.
［２］　第一フィルムと第二フィルムとの間に接着剤層を有し、
　前記接着剤層が［１］に記載の二液硬化型接着剤の硬化物からなる、積層フィルム。 [2] having an adhesive layer between the first film and the second film;
A laminated film, wherein the adhesive layer is a cured product of the two-component curing adhesive according to [1].
［３］　ポリイソシアネート（Ａ）を含み、かつ伸長粘度が０．１～１０Ｐａ・ｓであるポリイソシアネート組成物（Ｘ）を第一フィルムに塗布する第一塗工部と、
　ポリオール（Ｂ）を含み、かつ伸長粘度が０．１～１０Ｐａ・ｓであるポリオール組成物（Ｙ）を第二フィルムに塗布する第二塗工部と、
　前記第一フィルムの前記ポリイソシアネート組成物（Ｘ）の塗工面と、前記第二フィルムの前記ポリオール組成物（Ｙ）の塗工面とを貼り合わせる貼合装置とを有する、積層フィルムの製造装置。 [3] A first coating section that applies a polyisocyanate composition (X) containing a polyisocyanate (A) and having an elongational viscosity of 0.1 to 10 Pa s to the first film;
a second coating section for coating a second film with a polyol composition (Y) containing a polyol (B) and having an extensional viscosity of 0.1 to 10 Pa s;
An apparatus for producing a laminated film, comprising a lamination device for laminating the surface of the first film coated with the polyisocyanate composition (X) and the surface of the second film coated with the polyol composition (Y).
［４］　ポリイソシアネート（Ａ）を含み、かつ伸長粘度が０．１～１０Ｐａ・ｓであるポリイソシアネート組成物（Ｘ）を第一フィルムに塗布する第一塗布工程と、
　ポリオール（Ｂ）を含み、かつ伸長粘度が０．１～１０Ｐａ・ｓであるポリオール組成物（Ｙ）を第二フィルムに塗布する第二塗布工程とからなる二液分別塗布工程と、
　前記第一フィルムと前記第二フィルムとを積層することにより、前記第一フィルム上に塗布された前記ポリイソシアネート組成物（Ｘ）と、前記第二フィルム上に塗布された前記ポリオール組成物（Ｙ）とを接触させて硬化反応させる接着剤層形成工程とを有する、積層フィルムの製造方法。 [4] A first coating step of coating a first film with a polyisocyanate composition (X) containing a polyisocyanate (A) and having an elongational viscosity of 0.1 to 10 Pa s;
a two-liquid separate application step comprising a second application step of applying a polyol composition (Y) containing a polyol (B) and having an elongational viscosity of 0.1 to 10 Pa s on a second film;
By laminating the first film and the second film, the polyisocyanate composition (X) applied on the first film and the polyol composition (Y) applied on the second film ) and an adhesive layer forming step of contacting and curing reaction.
　本発明の二液硬化型接着剤は、伸長粘度が０．１～１０Ｐａ・ｓであるポリイソシアネート組成物（Ｘ）と、伸長粘度が０．１～１０Ｐａ・ｓであるポリオール組成物（Ｙ）との硬化反応を用いる二液硬化型接着剤である。本発明の二液硬化型接着剤は、ポリイソシアネート組成物（Ｘ）およびポリオール組成物（Ｙ）の伸長粘度が０．１～１０Ｐａ・ｓであり、初期凝集力に優れる。また、フィルム上に塗布する工程を行ってもミスティングが発生しにくい。 The two-component curing adhesive of the present invention comprises a polyisocyanate composition (X) having an elongational viscosity of 0.1 to 10 Pa s and a polyol composition (Y) having an elongational viscosity of 0.1 to 10 Pa s. It is a two-component curing adhesive that uses a curing reaction with In the two-component curing adhesive of the present invention, the polyisocyanate composition (X) and the polyol composition (Y) have extensional viscosities of 0.1 to 10 Pa·s, and are excellent in initial cohesive strength. In addition, misting is less likely to occur even when the process of coating the film is performed.
　このため、本発明の二液硬化型接着剤は、例えば、二液混合塗布工程を有する製造方法、二液分別塗布工程を有する製造方法などの製造方法を用いて、積層フィルムを製造する場合に好適に用いることができる。特に、二液分別塗布工程を有する方法を用いて、連続的に積層フィルムを製造する場合に好適に用いることができる。 For this reason, the two-component curing adhesive of the present invention can be used when manufacturing a laminated film using a manufacturing method such as a manufacturing method having a two-component mixed coating process and a manufacturing method having a two-component separate coating process. It can be used preferably. In particular, it can be suitably used when a laminated film is continuously produced using a method having a two-part separate coating process.
　本発明の積層フィルムは、第一フィルムと第二フィルムとの間に接着剤層を有し、接着剤層が本発明の二液硬化型接着剤の硬化物からなる。本発明の二液硬化型接着剤は、初期凝集力に優れるため、積層フィルムの製造工程におけるエージング時間を短縮したり、工程の選択の幅を広げたりすることができ、効率よく製造できる。また、本発明の積層フィルムは、フィルム上に塗布する工程を行ってもミスティングが発生しにくい本発明の二液硬化型接着剤を使用して製造できる。よって、本発明の積層フィルムは、例えば、二液混合塗布工程を有する製造方法、二液分別塗布工程を有する製造方法などの製造方法を用いて、効率よく製造できる。 The laminated film of the present invention has an adhesive layer between the first film and the second film, and the adhesive layer is made of the cured two-component curable adhesive of the present invention. Since the two-component curing adhesive of the present invention is excellent in initial cohesive strength, it is possible to shorten the aging time in the manufacturing process of the laminated film, widen the selection of processes, and efficiently manufacture the film. In addition, the laminated film of the present invention can be produced using the two-component curing adhesive of the present invention, which hardly causes misting even in the step of coating on the film. Therefore, the laminated film of the present invention can be efficiently manufactured using a manufacturing method including a two-component mixed coating process, a manufacturing method including a two-component separate coating process, and the like.
　本発明の積層フィルムの製造装置は、第一塗工部が、伸長粘度が０．１～１０Ｐａ・ｓであるポリイソシアネート組成物（Ｘ）を第一フィルムに塗布するものであり、第二塗工部が、伸長粘度が０．１～１０Ｐａ・ｓであるポリオール組成物（Ｙ）を第二フィルムに塗布するものである。このため、本発明の積層フィルムの製造装置は、本発明の液硬化型接着剤を使用して、二液分別塗布工程を有する製造方法により積層フィルムを製造する場合に、好適に使用できる。 In the laminated film manufacturing apparatus of the present invention, the first coating unit applies the polyisocyanate composition (X) having an extensional viscosity of 0.1 to 10 Pa s to the first film, and the second coating The working part applies the polyol composition (Y) having an extensional viscosity of 0.1 to 10 Pa·s to the second film. Therefore, the laminated film manufacturing apparatus of the present invention can be suitably used when manufacturing a laminated film using the liquid-curable adhesive of the present invention by a manufacturing method having a two-liquid separate coating process.
　本発明の積層フィルムの製造方法は、二液分別塗布工程を有し、第一塗布工程において、伸長粘度が０．１～１０Ｐａ・ｓであるポリイソシアネート組成物（Ｘ）を第一フィルムに塗布し、第二塗布工程において、伸長粘度が０．１～１０Ｐａ・ｓであるポリオール組成物（Ｙ）を第二フィルムに塗布する。このため、本発明の積層フィルムの製造方法では、本発明の初期凝集力に優れた二液硬化型接着剤を使用して、優れた特性を有する積層フィルムを、高い生産効率で製造できる。加えて、本発明の二液硬化型接着剤を使用することにより、二液硬化型接着剤をフィルム上に塗布することによるミスティングの発生を抑制しつつ、連続的に速いフィルム搬送速度で効率よく積層フィルムを製造できる。 The method for producing a laminated film of the present invention has a two-part separate coating step, and in the first coating step, the polyisocyanate composition (X) having an elongational viscosity of 0.1 to 10 Pa s is applied to the first film. Then, in the second coating step, the polyol composition (Y) having an extensional viscosity of 0.1 to 10 Pa·s is coated on the second film. Therefore, in the method for producing a laminated film of the present invention, a laminated film having excellent properties can be produced with high production efficiency using the two-component curing adhesive of the present invention having excellent initial cohesive strength. In addition, by using the two-component curable adhesive of the present invention, while suppressing the occurrence of misting due to applying the two-component curable adhesive on the film, it can be efficiently carried out at a continuously high film transport speed. Laminated films can be produced well.
図１は、本実施形態に係る積層フィルムの一例を示した断面図である。FIG. 1 is a cross-sectional view showing an example of the laminated film according to this embodiment. 図２は、本実施形態に係る積層フィルムの製造装置の正面図である。FIG. 2 is a front view of the laminated film manufacturing apparatus according to the present embodiment. 図３は、図２に示す積層フィルムの製造装置におけるポリオール塗工部の要部を示す正面図である。3 is a front view showing a main part of a polyol coating section in the laminated film manufacturing apparatus shown in FIG. 2. FIG. 図４は、図２に示す積層フィルムの製造装置におけるポリイソシアネート塗工部の要部を示す正面図である。4 is a front view showing a main part of a polyisocyanate coating section in the laminated film manufacturing apparatus shown in FIG. 2. FIG. 図５は、本実施形態の積層フィルムの製造に使用する製造装置の他の例を説明するための正面図である。FIG. 5 is a front view for explaining another example of the manufacturing apparatus used for manufacturing the laminated film of this embodiment.
　以下、本発明の二液硬化型接着剤、積層フィルム、積層フィルム製造装置、積層フィルムの製造方法について、図面を用いて詳細に説明する。なお、以下の説明で用いる図面は、本発明の特徴をわかりやすくするために、便宜上特徴となる部分を拡大して示している場合がある。このため、各構成要素の寸法比率などは、実際とは異なっている場合がある。 The two-component curing adhesive, laminated film, laminated film manufacturing apparatus, and laminated film manufacturing method of the present invention will be described in detail below with reference to the drawings. In the drawings used in the following description, in order to make it easier to understand the features of the present invention, there are cases where the feature portions are enlarged for the sake of convenience. Therefore, the dimensional ratio of each component may differ from the actual one.
［二液硬化型接着剤］
　本実施形態の二液硬化型接着剤は、ポリイソシアネート組成物（Ｘ）とポリオール組成物（Ｙ）との硬化反応を用いる二液硬化型接着剤である。
　本実施形態の二液硬化型接着剤におけるポリイソシアネート組成物（Ｘ）は、ポリイソシアネート（Ａ）を含み、かつ伸長粘度が０．１～１０Ｐａ・ｓである。ポリオール組成物（Ｙ）は、ポリオール（Ｂ）を含み、かつ伸長粘度が０．１～１０Ｐａ・ｓである。ポリイソシアネート組成物（Ｘ）は、必要に応じて、二液硬化型接着剤に含まれるポリオール（Ｂ）の一部を含んでいてもよい。
　本実施形態の二液硬化型接着剤は、ポリイソシアネート組成物（Ｘ）中のイソシアネート基と、ポリオール組成物（Ｙ）中の水酸基（または水酸基とアミノ基）との化学反応によって硬化する。 [Two-component curing adhesive]
The two-component curable adhesive of the present embodiment is a two-component curable adhesive using a curing reaction between the polyisocyanate composition (X) and the polyol composition (Y).
The polyisocyanate composition (X) in the two-component curing adhesive of the present embodiment contains the polyisocyanate (A) and has an elongational viscosity of 0.1 to 10 Pa·s. The polyol composition (Y) contains the polyol (B) and has an elongational viscosity of 0.1 to 10 Pa·s. The polyisocyanate composition (X) may contain part of the polyol (B) contained in the two-component curing adhesive, if necessary.
The two-component curable adhesive of this embodiment cures through a chemical reaction between the isocyanate groups in the polyisocyanate composition (X) and the hydroxyl groups (or hydroxyl groups and amino groups) in the polyol composition (Y).
（ポリイソシアネート組成物（Ｘ）およびポリオール組成物（Ｙ）の伸長粘度）
　本実施形態の二液硬化型接着剤は、ポリイソシアネート組成物（Ｘ）およびポリオール組成物（Ｙ）の伸長粘度が０．１～１０Ｐａ・ｓであり、初期凝集力に優れる。また、ポリイソシアネート組成物（Ｘ）およびポリオール組成物（Ｙ）の伸長粘度が０．１～１０Ｐａ・ｓであると、本実施形態の二液硬化型接着剤を用いて積層フィルムを製造する場合に、フィルム上にポリイソシアネート組成物（Ｘ）および／またはポリオール組成物（Ｙ）を塗布する工程を行っても、ミスティング（糸引き現象）が発生しにくい。このため、本実施形態の二液硬化型接着剤は、特に、ミスティングが発生しやすい二液分別塗布工程を有する方法を用いて積層フィルムを製造する場合に、好適に用いることができる。 (Elongational Viscosity of Polyisocyanate Composition (X) and Polyol Composition (Y))
The two-component curing adhesive of the present embodiment has an elongational viscosity of 0.1 to 10 Pa·s for the polyisocyanate composition (X) and the polyol composition (Y), and is excellent in initial cohesive strength. Further, when the extensional viscosity of the polyisocyanate composition (X) and the polyol composition (Y) is 0.1 to 10 Pa s, when producing a laminated film using the two-component curing adhesive of the present embodiment Furthermore, misting (stringing phenomenon) is less likely to occur even when the step of applying the polyisocyanate composition (X) and/or the polyol composition (Y) onto the film is performed. Therefore, the two-component curable adhesive of the present embodiment can be suitably used particularly when a laminated film is produced using a method having a two-component separate coating process in which misting is likely to occur.
　また、伸長粘度が０．１～１０Ｐａ・ｓであるポリイソシアネート組成物（Ｘ）と伸長粘度が０．１～１０Ｐａ・ｓであるポリオール組成物（Ｙ）とは、反応性が良好である。このため、二液硬化型接着剤のエージング温度を低くしたり、エージング時間を短縮したりでき、優れた特性を有する積層フィルムを高い生産効率で製造することが可能となる。
　ポリイソシアネート組成物（Ｘ）の伸長粘度は、後述するプレポリマーを含む組成物を用いる場合には、３Ｐａ・ｓ以上であることが好ましく、５Ｐａ・ｓ以上であることがより好ましく、７Ｐａ・ｓ以上であることがさらに好ましい。 Moreover, the polyisocyanate composition (X) having an elongational viscosity of 0.1 to 10 Pa·s and the polyol composition (Y) having an elongational viscosity of 0.1 to 10 Pa·s have good reactivity. As a result, the aging temperature of the two-component curing adhesive can be lowered and the aging time can be shortened, making it possible to produce laminated films having excellent properties with high production efficiency.
The elongational viscosity of the polyisocyanate composition (X) is preferably 3 Pa s or more, more preferably 5 Pa s or more, more preferably 7 Pa s when a composition containing a prepolymer to be described later is used. It is more preferable that it is above.
　ポリオール組成物（Ｙ）の伸長粘度は、ミスティングをより効果的に抑制できるとともに、ポリイソシアネート組成物（Ｘ）との反応性がより良好となって初期凝集力がより一層向上するため、７Ｐａ・ｓ以下が好ましく、５Ｐａ・ｓ以下がより好ましく、３Ｐａ・ｓ以下がさらに好ましく、２Ｐａ・ｓ以下が特に好ましい。ポリオール組成物（Ｙ）の伸長粘度が、１Ｐａ・ｓ以下であることも好ましい。 The elongational viscosity of the polyol composition (Y) can more effectively suppress misting and has better reactivity with the polyisocyanate composition (X) to further improve the initial cohesive strength. ·s or less is preferable, 5 Pa·s or less is more preferable, 3 Pa·s or less is even more preferable, and 2 Pa·s or less is particularly preferable. It is also preferable that the elongational viscosity of the polyol composition (Y) is 1 Pa·s or less.
　ポリイソシアネート組成物（Ｘ）およびポリオール組成物（Ｙ）は、ロールコーターもしくはグラビアコーターを用いて基材上に塗布されることが好ましい。このことから、ポリイソシアネート組成物（Ｘ）およびポリオール組成物（Ｙ）は、一定の伸長粘度を有することが好ましく、０．１Ｐａ・ｓ超であることが好ましく、０．２Ｐａ・ｓ超であることがより好ましい。
　また、二液硬化型接着剤の成形性を特に優先する場合には、ポリイソシアネート組成物（Ｘ）およびポリオール組成物（Ｙ）の伸長粘度を１Ｐａ・ｓ超とすることも好ましい。 Polyisocyanate composition (X) and polyol composition (Y) are preferably applied onto a substrate using a roll coater or gravure coater. For this reason, the polyisocyanate composition (X) and the polyol composition (Y) preferably have a constant elongational viscosity, preferably greater than 0.1 Pa s, and greater than 0.2 Pa s. is more preferable.
Moreover, when the moldability of the two-component curing adhesive is given priority, the elongational viscosity of the polyisocyanate composition (X) and the polyol composition (Y) is preferably more than 1 Pa·s.
　ポリイソシアネート組成物（Ｘ）の伸長粘度は、ポリイソシアネート組成物（Ｘ）に使用する材料（化合物）に含まれる低粘性材料と高粘性材料の比率を調整することにより、制御できる。
　なお、当業者であれば、ポリイソシアネート組成物（Ｘ）に使用する材料（化合物）の粘度を把握できる。また、当業者であれば、ポリイソシアネート組成物（Ｘ）に使用する材料（化合物）を組み合わせて、配合比を適宜調整することにより、通常の実験の範囲内で、公知の技術に基づいて、所望の範囲内の伸長粘度を有するポリイソシアネート組成物（Ｘ）を得ることができる。 The elongational viscosity of the polyisocyanate composition (X) can be controlled by adjusting the ratio of the low-viscosity material and the high-viscosity material contained in the materials (compounds) used in the polyisocyanate composition (X).
A person skilled in the art can grasp the viscosity of the material (compound) used for the polyisocyanate composition (X). Further, those skilled in the art can combine the materials (compounds) used in the polyisocyanate composition (X) and appropriately adjust the compounding ratio, within the scope of ordinary experiments, based on known techniques, A polyisocyanate composition (X) having an extensional viscosity within the desired range can be obtained.
　ポリオール組成物（Ｙ）の伸長粘度は、ポリオール組成物（Ｙ）に使用する材料（化合物）に含まれる低粘性材料と高粘性材料の比率を調整することにより、制御できる。
　なお、当業者であれば、ポリオール組成物（Ｙ）に使用する材料（化合物）の粘度を把握できる。また、当業者であれば、ポリオール組成物（Ｙ）に使用する材料（化合物）を組み合わせて、配合比を適宜調整することにより、通常の実験の範囲内で、公知の技術に基づいて、所望の範囲内の伸長粘度を有するポリオール組成物（Ｙ）を得ることができる。 The extensional viscosity of the polyol composition (Y) can be controlled by adjusting the ratio of the low-viscosity material and the high-viscosity material contained in the materials (compounds) used in the polyol composition (Y).
A person skilled in the art can grasp the viscosity of the material (compound) used for the polyol composition (Y). Further, those skilled in the art can combine the materials (compounds) used in the polyol composition (Y) and appropriately adjust the compounding ratio to achieve the desired result within the scope of ordinary experiments based on known techniques. A polyol composition (Y) having an extensional viscosity within the range of can be obtained.
（ポリイソシアネート（Ａ））
　ポリイソシアネート（Ａ）としては、特に限定なく公知のものを使用出来る。
　ポリイソシアネート（Ａ）としては、例えば、
　トリレンジイソシアネート、２，４’－ジフェニルメタンジイソシアネート（以下、ジフェニルメタンジイソシアネートを単に「ＭＤＩ」と記載する場合がある。）、２，２’－ＭＤＩ、４，４’－ＭＤＩ、１，５－ナフタレンジイソシアネート、トリフェニルメタントリイソシアネート等の芳香族ポリイソシアネート；
　キシリレンジイソシアネート、イソホロンジイソシアネート、４，４’－メチレンビス（シクロヘキシルイソシアネート）、１，３－（イソシアナートメチル）シクロヘキサン、１，６－ヘキサメチレンジイソシアネート、リジンジイソシアネート、トリメチルヘキサメチレンジイソシアネート等の脂肪族ポリイソシアネート；
　これらのポリイソシアネートのイソシアネート基（以下、「ＮＣＯ基」と称する場合がある。）の一部をカルボジイミドで変性した化合物；
　これらのポリイソシアネートに由来するイソシアヌレート体；これらのポリイソシアネートに由来するアロファネート体；これらのポリイソシアネートに由来するビゥレット体；これらのポリイソシアネートをトリメチロールプロパン変性したアダクト体；
　前記した各種のポリイソシアネートとポリオール成分との反応生成物（プレポリマー）であるポリイソシアネート（Ａ１）（以下、このプレポリマーであるポリイソシアネートを「ポリイソシアネート（Ａ１）」ということがある。）などが挙げられる。 (Polyisocyanate (A))
As the polyisocyanate (A), known ones can be used without particular limitation.
Examples of the polyisocyanate (A) include
tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate (hereinafter, diphenylmethane diisocyanate may be simply referred to as "MDI"), 2,2'-MDI, 4,4'-MDI, 1,5-naphthalene diisocyanate , aromatic polyisocyanates such as triphenylmethane triisocyanate;
Aliphatic polyisocyanates such as xylylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), 1,3-(isocyanatomethyl)cyclohexane, 1,6-hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate ;
Compounds in which a portion of the isocyanate groups (hereinafter sometimes referred to as "NCO groups") of these polyisocyanates are modified with carbodiimide;
isocyanurate compounds derived from these polyisocyanates; allophanate compounds derived from these polyisocyanates; biuret compounds derived from these polyisocyanates; adducts obtained by modifying these polyisocyanates with trimethylolpropane;
Polyisocyanate (A1), which is a reaction product (prepolymer) of the various polyisocyanates described above and a polyol component (hereinafter, this prepolymer polyisocyanate may be referred to as "polyisocyanate (A1)"), etc. is mentioned.
　ポリイソシアネート（Ａ１）において、芳香族ポリイソシアネート、脂肪族ポリイソシアネートと反応させるポリオール成分としては、具体的には、エチレングリコール、プロピレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、３－メチル－１，５－ペンタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコール、メチルペンタンジオール、ジメチルブタンジオール、ブチルエチルプロパンジオール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、ビスヒドロキシエトキシベンゼン等の鎖状脂肪族グリコール；１，４－シクロヘキサンジオール、１，４－シクロヘキサンジメタノール等の脂環式グリコール；グリセリン、トリメチロールプロパン、ペンタエリスリトール等の３官能又は４官能の脂肪族アルコール；ビスフェノールＡ、ビスフェノールＦ、水素添加ビスフェノールＡ、水素添加ビスフェノールＦ等のビスフェノール；ダイマージオール；前記グリコール、３官能又は４官能の脂肪族アルコール等の重合開始剤の存在下にエチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド、スチレンオキサイド、エピクロルヒドリン、テトラヒドロフラン、シクロヘキシレン等のアルキレンオキシドを付加重合したポリエーテルポリオール；プロピオラクトン、ブチロラクトン、ε－カプロラクトン、σ－バレロラクトン、β－メチル－σ－バレロラクトン等の環状エステル化合物の開環重合反応によって得られるポリエステルと、前記グリコール又は３官能若しくは４官能の脂肪族アルコールとの反応物であるポリエステルポリオール（１）； In the polyisocyanate (A1), specific examples of the polyol component to be reacted with the aromatic polyisocyanate and the aliphatic polyisocyanate include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1 ,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol , dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, and other chain aliphatic glycols; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and other alicyclic glycols; glycerin, trimethylolpropane, pentaerythritol Trifunctional or tetrafunctional aliphatic alcohol such as; Polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of agents; propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, A polyester polyol (1) which is a reaction product of a polyester obtained by a ring-opening polymerization reaction of a cyclic ester compound such as β-methyl-σ-valerolactone and the glycol or trifunctional or tetrafunctional aliphatic alcohol;
　前記鎖状脂肪族グリコール、脂環式グリコール、ダイマージオール、ビスフェノール又は前記ポリエーテルポリオール等のポリオールと、多価カルボン酸とを反応させて得られるポリエステルポリオール（２）；
　前記３官能又は４官能の脂肪族アルコールと、多価カルボン酸とを反応させて得られるポリエステルポリオール（３）；
　前記鎖状脂肪族グリコール、脂環式グリコール、ダイマージオール、ビスフェノール又は前記ポリエーテルポリオール等のポリオールと、前記３官能又は４官能の脂肪族アルコールと、多価カルボン酸とを反応させて得られるポリエステルポリオール（４）；
　ジメチロールプロピオン酸、ひまし油脂肪酸等のヒドロキシ酸の重合体である、ポリエステルポリオール（５）；
　ひまし油、脱水ひまし油、ひまし油の水素添加物であるひまし硬化油、ひまし油のアルキレンオキサイド５～５０モル付加体等のひまし油系ポリオール等、およびこれらの混合物等が挙げられる。 A polyester polyol (2) obtained by reacting a polyol such as the linear aliphatic glycol, alicyclic glycol, dimer diol, bisphenol, or polyether polyol with a polyvalent carboxylic acid;
polyester polyol (3) obtained by reacting the trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid;
A polyester obtained by reacting a polyol such as the chain aliphatic glycol, alicyclic glycol, dimer diol, bisphenol, or polyether polyol, the trifunctional or tetrafunctional aliphatic alcohol, and a polycarboxylic acid. polyol (4);
Polyester polyol (5), which is a polymer of hydroxy acids such as dimethylolpropionic acid and castor oil fatty acid;
Castor oil, dehydrated castor oil, hydrogenated castor oil, castor oil-based polyols such as adducts of 5 to 50 moles of alkylene oxide of castor oil, and mixtures thereof.
　前記ポリエステルポリオール（２）、（３）又は（４）の製造に用いられる多価カルボン酸としては、例えば、コハク酸、アジピン酸、アゼライン酸、セバシン酸、ドデカンジカルボン酸、無水マレイン酸、フマル酸等の非環状脂肪族ジカルボン酸；１，３－シクロペンタンジカルボン酸、１，４－シクロヘキサンジカルボン酸等の脂環式ジカルボン酸；テレフタル酸、イソフタル酸、フタル酸、１，４－ナフタレンジカルボン酸、２，５－ナフタレンジカルボン酸、２，６－ナフタレンジカルボン酸、ナフタル酸、ビフェニルジカルボン酸、１，２－ビス（フェノキシ）エタン－ｐ，ｐ’－ジカルボン酸等の芳香族系ジカルボン酸；これら脂肪族又は芳香族ジカルボン酸の無水物あるいはエステル形成性誘導体；ｐ－ヒドロキシ安息香酸、ｐ－（２－ヒドロキシエトキシ）安息香酸及びこれらのジヒドロキシカルボン酸のエステル形成性誘導体、ダイマー酸等の多塩基酸類が挙げられる。 Examples of the polyvalent carboxylic acid used for producing the polyester polyol (2), (3) or (4) include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, and fumaric acid. non-cyclic aliphatic dicarboxylic acids such as; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; Anhydrides or ester-forming derivatives of aromatic or aromatic dicarboxylic acids; p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids, polybasic acids such as dimer acid is mentioned.
　これらのポリイソシアネート（Ａ）の中でも、ポリイソシアネート（Ａ１）が好ましく、特に、前記ポリエーテルポリオールと前記ポリイソシアネートとを反応させることにより得られるポリイソシアネートが、濡れ性の点から好ましい。
　さらに、粘度が低く、低温での取り扱いの容易なポリイソシアネート（Ａ１）となることから、ポリイソシアネートと反応させるポリオール成分として、ポリプロピレン骨格を有するポリオールを用いることが好ましい。 Among these polyisocyanates (A), the polyisocyanate (A1) is preferred, and the polyisocyanate obtained by reacting the polyether polyol and the polyisocyanate is particularly preferred from the viewpoint of wettability.
Furthermore, it is preferable to use a polyol having a polypropylene skeleton as the polyol component to be reacted with the polyisocyanate, since the polyisocyanate (A1) has a low viscosity and is easy to handle at low temperatures.
　ポリイソシアネート（Ａ１）の硬化後の塗膜の柔軟性の観点から、ポリイソシアネートと反応させるポリオール成分として、数平均分子量（Ｍｎ）が３００～５，０００、より好ましくは３５０～３，０００のポリエーテルポリオールを用いることが好ましい。
　ポリオール成分に占める数平均分子量（Ｍｎ）が３００～５，０００のポリエーテルポリオールの割合は、一例として５０質量％以上であることが好ましい。ポリオール成分の全量が、数平均分子量（Ｍｎ）が３００～５，０００であるポリエーテルポリオールであってもよい。 From the viewpoint of the flexibility of the coating film after curing of the polyisocyanate (A1), the polyol component to be reacted with the polyisocyanate has a number average molecular weight (Mn) of 300 to 5,000, more preferably 350 to 3,000. Ether polyols are preferably used.
As an example, the proportion of polyether polyol having a number average molecular weight (Mn) of 300 to 5,000 in the polyol component is preferably 50% by mass or more. The total polyol component may be a polyether polyol having a number average molecular weight (Mn) of 300-5,000.
　本明細書において、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）は、下記条件のゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定される値である。
測定装置；東ソー株式会社製ＨＬＣ－８３２０ＧＰＣ
カラム；東ソー株式会社製ＴＳＫｇｅｌ　４０００ＨＸＬ、ＴＳＫｇｅｌ　３０００ＨＸＬ、ＴＳＫｇｅｌ　２０００ＨＸＬ、ＴＳＫｇｅｌ　１０００ＨＸＬ
検出器；ＲＩ（示差屈折計）
データ処理；東ソー株式会社製マルチステーションＧＰＣ－８０２０ｍｏｄｅｌＩＩ
測定条件；カラム温度４０℃
溶媒；テトラヒドロフラン
流速；０．３５ｍｌ／分
標準；単分散ポリスチレン
試料；樹脂固形分換算で０．２質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（１００μｌ） As used herein, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) under the following conditions.
Measuring device; HLC-8320GPC manufactured by Tosoh Corporation
Column; TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by Tosoh Corporation
Detector; RI (differential refractometer)
Data processing; Multi-station GPC-8020modelII manufactured by Tosoh Corporation
Measurement conditions; column temperature 40°C
Solvent; tetrahydrofuran flow rate; 0.35 ml/min standard; monodisperse polystyrene sample; 0.2% by mass of tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)
　ポリイソシアネート（Ａ１）において、ポリオール成分と反応させるポリイソシアネートとしては、後述するポリアミン（Ｃ）との反応性に優れることから、芳香族ポリイソシアネートを含むことが好ましい。芳香族ポリイソシアネートの配合量は、例えば、ポリイソシアネート（Ａ１）の合成時の仕込量合計１００質量部において、３０質量部以上であることが好ましく、４０質量部以上であることがより好ましい。芳香族ポリイソシアネートの配合量の上限については、保存安定性の観点から、６０質量部以下であることが好ましく、５５質量部以下であることがより好ましい。 In the polyisocyanate (A1), the polyisocyanate to be reacted with the polyol component preferably contains an aromatic polyisocyanate because of its excellent reactivity with the polyamine (C) described later. The amount of the aromatic polyisocyanate to be blended is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, for 100 parts by mass of the total charged amount for synthesizing the polyisocyanate (A1). From the viewpoint of storage stability, the upper limit of the amount of the aromatic polyisocyanate compounded is preferably 60 parts by mass or less, more preferably 55 parts by mass or less.
　ポリオール成分と反応させるポリイソシアネートは、保存安定性の観点から脂肪族ポリイソシアネート、脂肪族ポリイソシアネートの誘導体の少なくとも一種を、芳香族ポリイソシアネートと併用することが好ましい。 Regarding the polyisocyanate to be reacted with the polyol component, it is preferable to use at least one of aliphatic polyisocyanate and aliphatic polyisocyanate derivative together with aromatic polyisocyanate from the viewpoint of storage stability.
　ポリイソシアネート（Ａ１）における前記したポリイソシアネートとポリオール成分との反応割合は、ポリイソシアネート中のイソシアネート基とポリオール成分中の水酸基との当量比［イソシアネート基／水酸基］が１．５～５．０の範囲であることが好ましい。このようなポリイソシアネート（Ａ１）を採用したポリイソシアネート（Ａ）は、これを含むポリイソシアネート組成物（Ｘ）の粘度が適正範囲となって、塗工性が良好になるとともに、ポリイソシアネート（Ａ）を含む二液硬化型接着剤からなる塗膜の凝集力が良好となるため、好ましい。 The reaction ratio of the polyisocyanate and the polyol component in the polyisocyanate (A1) is such that the equivalent ratio [isocyanate group/hydroxyl group] between the isocyanate group in the polyisocyanate and the hydroxyl group in the polyol component is 1.5 to 5.0. A range is preferred. The polyisocyanate (A) employing such a polyisocyanate (A1) has an appropriate viscosity of the polyisocyanate composition (X) containing it, and the coating property is improved, and the polyisocyanate (A ) is preferable because the cohesive force of the coating film made of the two-component curing adhesive containing is improved.
　ポリイソシアネート（Ａ）は、重量平均分子量（Ｍｗ）が１００～１０，０００の範囲であることが、エージング時間を短くしつつ、適正な実包性を確保できる点から好ましく、２００～５，０００の範囲であることがより好ましい。
　ポリイソシアネート（Ａ）がポリイソシアネート（Ａ１）の場合には、重量平均分子量（Ｍｗ）が３００～１０，０００の範囲であることが好ましい。 The polyisocyanate (A) preferably has a weight average molecular weight (Mw) in the range of 100 to 10,000 from the viewpoint of shortening the aging time and ensuring proper packaging properties. A range is more preferred.
When the polyisocyanate (A) is the polyisocyanate (A1), it preferably has a weight average molecular weight (Mw) in the range of 300 to 10,000.
　ポリイソシアネート（Ａ）は、イソシアネート含有率が５～２０質量％であることが好ましい。このようなポリイソシアネート（Ａ）を含むポリイソシアネート組成物（Ｘ）は、適正な樹脂粘度となって、塗工性に優れる点から好ましい。
　ポリイソシアネート（Ａ）のイソシアネート含有率は、ジ－ｎ－ブチルアミンを使用した滴定法によって求めた値である。 The polyisocyanate (A) preferably has an isocyanate content of 5 to 20% by mass. The polyisocyanate composition (X) containing such a polyisocyanate (A) is preferable because it has an appropriate resin viscosity and is excellent in coatability.
The isocyanate content of polyisocyanate (A) is a value determined by a titration method using di-n-butylamine.
（ポリオール（Ｂ））
　ポリオール（Ｂ）としては、例えば、エチレングリコール、プロピレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、３－メチル－１，５－ペンタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコール、メチルペンタンジオール、ジメチルブタンジオール、ブチルエチルプロパンジオール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、ビスヒドロキシエトキシベンゼン、１，４－シクロヘキサンジオール、１，４－シクロヘキサンジメタノール、トリエチレングリコール等のグリコール； (Polyol (B))
Examples of the polyol (B) include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6 - hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol , 1,4-cyclohexanedimethanol, glycols such as triethylene glycol;
　グリセリン、トリメチロールプロパン、ペンタエリスリトール等の３官能又は４官能の脂肪族アルコール；ビスフェノールＡ、ビスフェノールＦ、水素添加ビスフェノールＡ、水素添加ビスフェノールＦ等のビスフェノール；ダイマージオール；前記グリコール、３官能又は４官能の脂肪族アルコール等の重合開始剤の存在下にエチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド、スチレンオキサイド、エピクロルヒドリン、テトラヒドロフラン、シクロヘキシレン等のアルキレンオキシドを付加重合したポリエーテルポリオール；該ポリエーテルポリオールを更に前記芳香族又は脂肪族ポリイソシアネートで高分子量化したポリエーテルウレタンポリオール；プロピオラクトン、ブチロラクトン、ε－カプロラクトン、σ－バレロラクトン、β－メチル－σ－バレロラクトン等の環状エステル化合物の開環重合反応によって得られるポリエステルと前記グリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール等の多価アルコールとの反応物であるポリエステルポリオール（１）； trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, and pentaerythritol; bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F; dimer diols; A polyether polyol obtained by addition polymerization of an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of a polymerization initiator such as an aliphatic alcohol; Polyether urethane polyol polymerized with aromatic or aliphatic polyisocyanate; ring-opening polymerization reaction of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone A polyester polyol (1) which is a reaction product of a polyester obtained by and a polyhydric alcohol such as the glycol, glycerin, trimethylolpropane, pentaerythritol;
　前記グリコール、ダイマージオール、又はビスフェノール等の２官能型ポリオールと、多価カルボン酸とを反応させて得られるポリエステルポリオール（２）；
　前記３官能又は４官能の脂肪族アルコールと、多価カルボン酸とを反応させて得られるポリエステルポリオール（３）；
　２官能型ポリオールと、前記３官能又は４官能の脂肪族アルコールと、多価カルボン酸とを反応させて得られるポリエステルポリオール（４）；
　ジメチロールプロピオン酸、ひまし油脂肪酸等のヒドロキシ酸の重合体である、ポリエステルポリオール（５）；
　前記ポリエステルポリオール（１）～（５）と前記ポリエーテルポリオールと芳香族若しくは脂肪族ポリイソシアネートとを反応させて得られるポリエステルポリエーテルポリオール；
　前記ポリエステルポリオール（１）～（５）を芳香族若しくは脂肪族ポリイソシアネートで高分子量化して得られるポリエステルポリウレタンポリオール；
　ひまし油、脱水ひまし油、ひまし油の水素添加物であるひまし硬化油、ひまし油のアルキレンオキサイド５～５０モル付加体等のひまし油系ポリオール等、及びこれらの混合物等が挙げられる。 a polyester polyol (2) obtained by reacting a bifunctional polyol such as the glycol, dimer diol, or bisphenol with a polyvalent carboxylic acid;
polyester polyol (3) obtained by reacting the trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid;
A polyester polyol (4) obtained by reacting a bifunctional polyol, the trifunctional or tetrafunctional aliphatic alcohol, and a polyvalent carboxylic acid;
Polyester polyol (5), which is a polymer of hydroxy acids such as dimethylolpropionic acid and castor oil fatty acid;
Polyester polyether polyols obtained by reacting the polyester polyols (1) to (5), the polyether polyols, and an aromatic or aliphatic polyisocyanate;
polyester polyurethane polyols obtained by polymerizing the polyester polyols (1) to (5) with aromatic or aliphatic polyisocyanates;
Castor oil, dehydrated castor oil, hydrogenated castor oil, castor oil-based polyols such as adducts of 5 to 50 moles of alkylene oxide of castor oil, and mixtures thereof.
　前記ポリエステルポリオール（２）、（３）又は（４）の製造に用いられる多価カルボン酸としては、例えば、コハク酸、アジピン酸、アゼライン酸、セバシン酸、ドデカンジカルボン酸、無水マレイン酸、フマル酸、１，３－シクロペンタンジカルボン酸、１，４－シクロヘキサンジカルボン酸等の脂肪族ジカルボン酸；テレフタル酸、イソフタル酸、１，４－ナフタレンジカルボン酸、２，５－ナフタレンジカルボン酸、２，６－ナフタレンジカルボン酸、ナフタル酸、ビフェニルジカルボン酸、１，２－ビス（フェノキシ）エタン－ｐ，ｐ’－ジカルボン酸等の芳香族ジカルボン酸；及びこれら脂肪族又はジカルボン酸の無水物あるいはエステル形成性誘導体；ｐ－ヒドロキシ安息香酸、ｐ－（２－ヒドロキシエトキシ）安息香酸及びこれらのジヒドロキシカルボン酸のエステル形成性誘導体、ダイマー酸等の多塩基酸類が挙げられる。 Examples of the polyvalent carboxylic acid used for producing the polyester polyol (2), (3) or (4) include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, and fumaric acid. , 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and other aliphatic dicarboxylic acids; terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6- Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; and anhydrides or ester-forming derivatives of these aliphatic or dicarboxylic acids polybasic acids such as p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, ester-forming derivatives of these dihydroxycarboxylic acids, and dimer acid.
　ポリオール（Ｂ）としては、複数の水酸基を有する３級アミン化合物を使用してもよい。複数の水酸基を有する３級アミン化合物は、水酸基がポリイソシアネート（Ａ）と反応して硬化するのみならず、アミン構造が硬化反応を促進することから硬化促進剤としても機能する。
　複数の水酸基を有する３級アミン化合物において、水酸基の数は２個以上であり、２～６個であることが好ましい。複数の水酸基を有する３級アミン化合物は、３級アミノ基を１つ以上有していればよく、１～２個有していることが好ましい。 A tertiary amine compound having a plurality of hydroxyl groups may be used as the polyol (B). A tertiary amine compound having a plurality of hydroxyl groups not only cures when the hydroxyl groups react with the polyisocyanate (A), but also functions as a curing accelerator because the amine structure accelerates the curing reaction.
In the tertiary amine compound having a plurality of hydroxyl groups, the number of hydroxyl groups is 2 or more, preferably 2 to 6. A tertiary amine compound having a plurality of hydroxyl groups may have one or more tertiary amino groups, preferably one or two.
　複数の水酸基を有する３級アミン化合物としては、具体的には、ポリプロピレングリコールエチレンジアミンエーテル、トリ（１，２－ポリプロピレングリコール）アミン、Ｎ－エチルジエタノールアミン、Ｎ－メチル－Ｎ－ヒドロキシエチル－Ｎ－ヒドロキシエトキシエチルアミン、ペンタキスヒドロキシプロピルジエチレントリアミン、テトラキスヒドロキシプロピルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラキス（２－ヒドロキシプロピル）エチレンジアミン、トリエタノールアミン、トリエタノールアミンプロポキシレーティッド等が挙げられる。 Specific examples of tertiary amine compounds having a plurality of hydroxyl groups include polypropylene glycol ethylene diamine ether, tri(1,2-polypropylene glycol) amine, N-ethyldiethanolamine, N-methyl-N-hydroxyethyl-N-hydroxy ethoxyethylamine, pentakishydroxypropyldiethylenetriamine, tetrakishydroxypropylethylenediamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, triethanolamine, triethanolamine propoxylated and the like.
　複数の水酸基を有する３級アミン化合物としては、市販品を使用してもよい。市販品としては、例えば、株式会社ＡＤＥＫＡ製のＥＤＰ－３００、国都化工社製のＥＤ－５００やＴＥ－３６０、ＤＯＷ社製　ＶＯＲＡＮＯＬ　ＴＭ８００Ｐｏｌｙｏｌ等が挙げられる。 A commercially available product may be used as the tertiary amine compound having multiple hydroxyl groups. Examples of commercially available products include EDP-300 manufactured by ADEKA Corporation, ED-500 and TE-360 manufactured by Kokuto Kako, and VORANOL TM800 Polyol manufactured by DOW.
　ポリオール（Ｂ）が複数の水酸基を有する３級アミン化合物を含む場合、ポリオール（Ｂ）中における３級アミン化合物以外のポリオールと、３級アミン化合物との配合割合（３級アミン化合物以外のポリオール／３級アミン化合物（質量比））は、１００／５～１００／７０であることが好ましく、１００／１０～１００／７０であることがより好ましい。 When the polyol (B) contains a tertiary amine compound having a plurality of hydroxyl groups, the mixing ratio of the polyol other than the tertiary amine compound in the polyol (B) and the tertiary amine compound (polyol other than the tertiary amine compound/ The tertiary amine compound (mass ratio)) is preferably from 100/5 to 100/70, more preferably from 100/10 to 100/70.
　ポリオール（Ｂ）としては、これらの化合物を単独もしくは複数組み合わせて用いることができる。
　ポリオール（Ｂ）は、ポリエーテル骨格を有するポリオールを含むことが好ましく、特にポリプロピレン骨格を有するポリオールを含むことが好ましい。このようなポリオール（Ｂ）は、無溶剤型であっても２５℃～６０℃の温度で塗工可能な粘度となる。また、このようなポリオール（Ｂ）を含む二液硬化型接着剤は、シリカおよび／またはアルミナ等の金属酸化物、アルミニウム等の金属、および樹脂フィルムとの接着強度に優れるものとなり、好ましい。 As polyol (B), these compounds can be used singly or in combination.
Polyol (B) preferably contains a polyol having a polyether skeleton, and more preferably contains a polyol having a polypropylene skeleton. Such a polyol (B) has a viscosity that enables coating at a temperature of 25° C. to 60° C. even if it is a non-solvent type. In addition, the two-component curing adhesive containing such a polyol (B) is preferable because it exhibits excellent adhesion strength to metal oxides such as silica and/or alumina, metals such as aluminum, and resin films.
　ポリエーテル骨格を有するポリオールの含有量は、塗工適性の観点からポリオール（Ｂ）全量に対して、５質量％以上であることが好ましく、１０質量％以上であることがより好ましく、１５質量％以上であることがより好ましい。ポリエーテル骨格を有するポリオールの含有量の上限については、特に制限されず、ポリオール（Ｂ）の全量がポリエーテル骨格を有するポリオールであってもよいが、二液硬化型接着剤の初期凝集力の観点から９５質量％以下であることが好ましい。 The content of the polyol having a polyether skeleton is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass, based on the total amount of the polyol (B) from the viewpoint of coatability. It is more preferable to be above. The upper limit of the content of the polyol having a polyether skeleton is not particularly limited, and the total amount of the polyol (B) may be a polyol having a polyether skeleton. From the viewpoint, it is preferably 95% by mass or less.
　ポリオール（Ｂ）は、二液硬化型接着剤の初期凝集力および塗工適性の観点から、ひまし油、脱水ひまし油、ひまし油の水素添加物であるひまし硬化油、ひまし油のアルキレンオキサイド５～５０モル付加体等のひまし油系ポリオールからなる群から選ばれる少なくとも１種のひまし油系化合物を含むことが好ましい。これらのひまし油系化合物は、ポリオール（Ｂ）全量に対して５質量％以上であることが好ましく、１０質量％以上であることがより好ましく、１５質量％以上であることがより好ましく、２０質量％以上であることがより好ましい。また、ひまし油系化合物の上限については、特に制限されず、ポリオール（Ｂ）の全量がひまし油系化合物であってもよいが、塗工適性の観点からは９５質量％以下であることが好ましい。 Polyol (B) is castor oil, dehydrated castor oil, hydrogenated castor oil that is a hydrogenated product of castor oil, and 5 to 50 moles of alkylene oxide added to castor oil, from the viewpoint of the initial cohesive strength and coatability of the two-component curing adhesive. It preferably contains at least one castor oil-based compound selected from the group consisting of castor oil-based polyols such as castor oil-based polyols. These castor oil-based compounds are preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass or more, and 20% by mass of the total amount of polyol (B). It is more preferable to be above. Also, the upper limit of the castor oil-based compound is not particularly limited, and the total amount of the polyol (B) may be a castor oil-based compound, but from the viewpoint of coatability, it is preferably 95% by mass or less.
　ポリオール（Ｂ）は、反応性の高い低分子量のポリオール（常温で液体、分子量が１５０以下程度のもの）を含んでいてもよい。このような低分子量のポリオールを含むことにより、ポリイソシアネート（Ａ）との反応を早くできる。一方で、低分子量のポリオールの配合量が多すぎると、ポリイソシアネート（Ａ）との反応が早くなりすぎるおそれがある。このため、低分子量のポリオールの含有量は、ポリオール（Ｂ）の５質量％以下であることが好ましく、より好ましくは３質量％以下である。 The polyol (B) may contain a highly reactive low-molecular-weight polyol (liquid at room temperature and having a molecular weight of about 150 or less). By containing such a low-molecular-weight polyol, the reaction with the polyisocyanate (A) can be accelerated. On the other hand, if the amount of the low-molecular-weight polyol is too large, the reaction with the polyisocyanate (A) may be too fast. Therefore, the content of the low-molecular-weight polyol is preferably 5% by mass or less, more preferably 3% by mass or less, of the polyol (B).
　ポリオール（Ｂ）の重量平均分子量（Ｍｗ）は、４００～５０００であると、適正な粘度範囲となるため塗工性が良好になるとともに、二液硬化型接着剤の凝集力が良好となり、好ましい。 When the weight-average molecular weight (Mw) of the polyol (B) is 400 to 5000, the viscosity is in an appropriate range, so the coatability is improved, and the cohesive force of the two-component curing adhesive is improved, which is preferable. .
　ポリオール（Ｂ）の水酸基価は、５０ｍｇＫＯＨ／ｇ以上３００ｍｇＫＯＨ／ｇ以下であることが好ましく、１００ｍｇＫＯＨ／ｇ以上２５０ｍｇＫＯＨ／ｇ以下であることがより好ましい。
　ポリオール（Ｂ）の水酸基価は、ＪＩＳ－Ｋ００７０に記載の水酸基価測定方法にて測定できる。 The hydroxyl value of the polyol (B) is preferably 50 mgKOH/g or more and 300 mgKOH/g or less, more preferably 100 mgKOH/g or more and 250 mgKOH/g or less.
The hydroxyl value of the polyol (B) can be measured by the hydroxyl value measuring method described in JIS-K0070.
（ポリアミン（Ｃ））
　ポリオール組成物（Ｙ）は、ポリアミン（Ｃ）を含むことが好ましい。ポリアミン（Ｃ）は硬化促進剤として機能する。
　ポリアミン（Ｃ）としては、特に限定なく公知のものを使用できる。ポリアミン（Ｃ）は、二液硬化型接着剤からなる塗膜の強靭さを保つために、分子内にアミノ基（ＮＨ２基、ＮＨＲ基（Ｒは、アルキル基を示す。））を２つ以上有する化合物であることが望ましい。 (Polyamine (C))
The polyol composition (Y) preferably contains a polyamine (C). Polyamine (C) functions as a curing accelerator.
As the polyamine (C), known ones can be used without particular limitation. Polyamine (C) has two amino groups ( NH2 group, NHR group (R represents an alkyl group)) in the molecule in order to maintain the toughness of the coating film made of a two-component curing adhesive. It is desirable that the compound has the above.
　ポリアミン（Ｃ）としては、例えば、メチレンジアミン、エチレンジアミン、イソホロンジアミン、３，９－ジプロパンアミン－２，４，８，１０－テトラオキサスピロドウンデカン、リシン、フェニレンジアミン、２，２，４－トリメチルヘキサメチレンジアミン、トリレンジアミン、ヒドラジン、ピペラジン、ヘキサメチレンジアミン、プロピレンジアミン、ジシクロヘキシルメタン－４，４－ジアミン、２－ヒドロキシエチルエチレンジアミン、ジ－２－ヒドロキシエチルエチレンジアミン、ジ－２－ヒドロキシエチルプロピレンジアミン、２－ヒドロキシプロピルエチレンジアミン、又はジ－２－ヒドロキシプロピルエチレンジアミン、ポリ（プロピレングリコール）ジアミン、ポリ（プロピレングリコール）トリアミン、ポリ（プロピレングリコール）テトラアミン、１，２－ジアミノプロパン、１，３－ジアミノプロパン、 Examples of the polyamine (C) include methylenediamine, ethylenediamine, isophoronediamine, 3,9-dipropanamine-2,4,8,10-tetraoxapyrodundecane, lysine, phenylenediamine, 2,2,4- trimethylhexamethylenediamine, tolylenediamine, hydrazine, piperazine, hexamethylenediamine, propylenediamine, dicyclohexylmethane-4,4-diamine, 2-hydroxyethylethylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylene diamine, 2-hydroxypropylethylenediamine, or di-2-hydroxypropylethylenediamine, poly(propylene glycol) diamine, poly(propylene glycol) triamine, poly(propylene glycol) tetraamine, 1,2-diaminopropane, 1,3-diamino propane,
　１，４－ジアミノブタン、１，５－ジアミノペンタン、１，６－ジアミノヘキサン、１，７－ジアミノヘプタン、１，８－ジアミノオクタン、１，９－ジアミノノナン、１，１０－ジアミノデカン等、ベンジルアミン、ジエチレントリアミン、ジプロピレントリアミン、トリエチレンテトラミン、トリプロピレンテトラミン、テトラエチレンペンタミン、テトラプロピレンペンタミン、ペンタエチレンヘキサミン、ノナエチレンデカミン、トリメチルヘキサメチレンジアミン等、テトラ（アミノメチル）メタン、テトラキス（２－アミノエチルアミノメチル）メタン、１，３－ビス（２’－アミノエチルアミノ）プロパン、トリエチレン－ビス（トリメチレン）ヘキサミン、ビス（３－アミノエチル）アミン、ビスヘキサメチレントリアミン等、１，４－シクロヘキサンジアミン、４，４’－メチレンビスシクロヘキシルアミン、４，４’－イソプロピリデンビスシクロヘキシルアミン、ノルボルナジアミン、 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, etc., benzyl amine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, trimethylhexamethylenediamine, etc., tetra(aminomethyl)methane, tetrakis ( 2-aminoethylaminomethyl)methane, 1,3-bis(2′-aminoethylamino)propane, triethylene-bis(trimethylene)hexamine, bis(3-aminoethyl)amine, bishexamethylenetriamine, etc., 1, 4-cyclohexanediamine, 4,4′-methylenebiscyclohexylamine, 4,4′-isopropylidenebiscyclohexylamine, norbornadiamine,
　ビス（アミノメチル）シクロヘキサン、ジアミノジシクロヘキシルメタン、イソホロンジアミン、メンセンジアミン等、ビス（アミノアルキル）ベンゼン、ビス（アミノアルキル）ナフタレン、ビス（シアノエチル）ジエチレントリアミン、オルトキシリレンジアミン、メタキシリレンジアミン、パラキシリレンジアミン、フェニレンジアミン、ナフチレンジアミン、ジアミノジフェニルメタン、ジアミノジエチルフェニルメタン、２，２－ビス（４－アミノフェニル）プロパン、４，４’－ジアミノジフェニルエーテル、４，４’－ジアミノベンゾフェノン、４，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルスルホン、２，２’－ジメチル－４，４’－ジアミノジフェニルメタン、２，４’－ジアミノビフェニル、２，３’－ジメチル－４，４’－ジアミノビフェニル、３，３’－ジメトキシ－４，４’－ジアミノビフェニル、ビス（アミノメチル）ナフタレン、ビス（アミノエチル）ナフタレン等、Ｎ－メチルピペラジン、モルホリン、１，４－ビス－（８－アミノプロピル）－ピペラジン、ピペラジン－１，４－ジアザシクロヘプタン、１－（２’－アミノエチルピペラジン）、１－［２’－（２”－アミノエチルアミノ）エチル］ピペラジン、トリシクロデカンジアミン、前記した各種のポリアミンと前記した各種のイソシアネート成分との反応生成物であるポリウレアアミンなどが挙げられる。 Bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, isophoronediamine, menzenediamine, etc., bis(aminoalkyl)benzene, bis(aminoalkyl)naphthalene, bis(cyanoethyl)diethylenetriamine, orthoxylylenediamine, metaxylylenediamine, para xylylenediamine, phenylenediamine, naphthylenediamine, diaminodiphenylmethane, diaminodiethylphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 2,4'-diaminobiphenyl, 2,3'-dimethyl-4,4'- Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, bis(aminomethyl)naphthalene, bis(aminoethyl)naphthalene, etc., N-methylpiperazine, morpholine, 1,4-bis-(8-amino propyl)-piperazine, piperazine-1,4-diazacycloheptane, 1-(2′-aminoethylpiperazine), 1-[2′-(2″-aminoethylamino)ethyl]piperazine, tricyclodecanediamine, Examples include polyureaamine, which is a reaction product of various polyamines described above and various isocyanate components described above.
　ポリアミン（Ｃ）としては、二液硬化型接着剤からなる塗膜の柔軟性を保つために、主鎖にポリエーテル構造を有するポリエーテルアミンを用いることが好ましい。
　これらのポリアミン（Ｃ）は、単独で用いても良いし、２種類以上を併用しても良い。 As the polyamine (C), it is preferable to use a polyetheramine having a polyether structure in the main chain in order to maintain the flexibility of the coating film composed of the two-component curing adhesive.
These polyamines (C) may be used alone or in combination of two or more.
　ポリアミン（Ｃ）としては、市販品を使用してもよい。市販品としては、ＢＡＳＦ社製のＥＣ－３１０、ＥＣ－３０３等が挙げられる。 A commercially available product may be used as the polyamine (C). Commercially available products include EC-310 and EC-303 manufactured by BASF.
　ポリイソシアネート組成物（Ｘ）中の官能基（ポリイソシアネート（Ａ）の有するイソシアネート基）と、ポリオール組成物（Ｙ）中の官能基（ポリオール（Ｂ）の有する水酸基、ポリアミン（Ｃ）の有するアミノ基）のモル比［イソシアネート基／（水酸基＋アミノ基）］は、０．５～５．０であることが望ましく、二液硬化型接着剤の接着性能の観点から１．０～３．０の範囲であることが更に望ましい。 The functional group in the polyisocyanate composition (X) (the isocyanate group of the polyisocyanate (A)) and the functional group in the polyol composition (Y) (the hydroxyl group of the polyol (B), the amino group of the polyamine (C), group) molar ratio [isocyanate group / (hydroxyl group + amino group)] is preferably 0.5 to 5.0, and from the viewpoint of the adhesive performance of the two-component curing adhesive, 1.0 to 3.0 is more desirable.
　ポリオール組成物（Ｙ）中のポリオール（Ｂ）とポリアミン（Ｃ）との割合は、ポリアミン（Ｃ）由来のアミノ基とポリオール（Ｂ）由来の水酸基とのモル比［アミノ基／水酸基］が０．００１～２．０であることが望ましく、二液硬化型接着剤の接着強度と加工外観と加工性の実用性を両立させる観点で、０．１～１．０の範囲であることがより好ましい。上記モル比が０．００１以上であると、二液硬化型接着剤を用いて製造した積層フィルムの加工性が良好となる。上記モル比が２．０以下であると、二液硬化型接着剤の接着強度が良好となる。 The ratio of the polyol (B) and the polyamine (C) in the polyol composition (Y) is such that the molar ratio [amino group/hydroxyl group] of the amino group derived from the polyamine (C) and the hydroxyl group derived from the polyol (B) is 0. .001 to 2.0 is desirable, and from the viewpoint of achieving both the adhesive strength of the two-part curing adhesive, the processed appearance, and the practicality of workability, the range of 0.1 to 1.0 is more preferable. preferable. When the above molar ratio is 0.001 or more, the workability of the laminated film produced using the two-component curing adhesive becomes favorable. When the molar ratio is 2.0 or less, the adhesion strength of the two-component curing adhesive becomes favorable.
（溶剤）
　本実施形態の二液硬化型接着剤は、無溶剤型の接着剤として使用できるが、本実施形態の二液硬化型接着剤は、必要に応じて、溶剤を含有していてもよい。
　本実施形態において「溶剤」とは、ポリイソシアネート組成物（Ｘ）および／またはポリオール組成物（Ｙ）を溶解できる溶解性の高い有機溶剤を指す。また、本実施形態において「無溶剤」であるとは、これらの溶解性の高い有機溶剤を含まないことを指す。 (solvent)
The two-component curable adhesive of the present embodiment can be used as a solventless adhesive, but the two-component curable adhesive of the present embodiment may contain a solvent if necessary.
In the present embodiment, the "solvent" refers to a highly soluble organic solvent capable of dissolving the polyisocyanate composition (X) and/or the polyol composition (Y). Further, in the present embodiment, "solvent-free" refers to not containing these highly soluble organic solvents.
　溶解性の高い有機溶剤（溶剤）としては、具体的には、トルエン、キシレン、塩化メチレン、テトラヒドロフラン、メタノール、エタノール、イソプロピルアルコール、酢酸メチル、酢酸エチル、酢酸ｎ－ブチル、アセトン、メチルエチルケトン（ＭＥＫ）、シクロヘキサノン、ｎ－ヘキサン、シクロヘキサン等が挙げられる。これらの中でも、トルエン、キシレン、塩化メチレン、テトラヒドロフラン、酢酸メチル、酢酸エチルは、特に溶解性の高い有機溶剤である。 Specific examples of highly soluble organic solvents (solvents) include toluene, xylene, methylene chloride, tetrahydrofuran, methanol, ethanol, isopropyl alcohol, methyl acetate, ethyl acetate, n-butyl acetate, acetone, and methyl ethyl ketone (MEK). , cyclohexanone, n-hexane, cyclohexane, and the like. Among these, toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, and ethyl acetate are particularly highly soluble organic solvents.
　本実施形態の二液硬化型接着剤は、粘度を低くする要求がある場合には、所望の粘度となるように、溶剤を用いて希釈して使用できる。その場合、溶剤を用いて、ポリイソシアネート組成物（Ｘ）またはポリオール組成物（Ｙ）のうち一方のみを希釈してもよいし、両方を希釈してもよい。 The two-component curable adhesive of this embodiment can be used by diluting it with a solvent so as to obtain the desired viscosity when it is required to lower the viscosity. In that case, a solvent may be used to dilute either one of the polyisocyanate composition (X) or the polyol composition (Y), or both.
　本実施形態の二液硬化型接着剤に含有してもよい有機溶剤としては、例えば、メタノール、エタノール、イソプロピルアルコール、酢酸メチル、酢酸エチル、酢酸ｎ－ブチル、アセトン、メチルエチルケトン（ＭＥＫ）、シクロヘキサノン、トルエン、キシレン、ｎ－ヘキサン、シクロヘキサン等が挙げられる。これらの中でも、ポリイソシアネート組成物（Ｘ）およびポリオール組成物（Ｙ）の溶解性の点から、酢酸エチルおよび／またはメチルエチルケトン（ＭＥＫ）を用いることが好ましく、特に、酢酸エチルを用いることが好ましい。
　本実施形態の二液硬化型接着剤における有機溶剤の含有量は、要求される粘度によって適宜決定することができ、例えば、２０～５０質量％とすることができる。 Examples of organic solvents that may be contained in the two-component curing adhesive of the present embodiment include methanol, ethanol, isopropyl alcohol, methyl acetate, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, Examples include toluene, xylene, n-hexane, cyclohexane and the like. Among these, it is preferable to use ethyl acetate and/or methyl ethyl ketone (MEK), and it is particularly preferable to use ethyl acetate, from the viewpoint of the solubility of the polyisocyanate composition (X) and the polyol composition (Y).
The content of the organic solvent in the two-component curing adhesive of the present embodiment can be appropriately determined according to the required viscosity, and can be, for example, 20 to 50% by mass.
（触媒）
　本実施形態の二液硬化型接着剤は、触媒を含有していてもよい。触媒は、ポリイソシアネート組成物（Ｘ）とポリオール組成物（Ｙ）のいずれか一方にのみ含まれていてもよいし、両方に含まれていてもよい。触媒は、一般的にポリイソシアネート組成物との反応性が高く、ポリイソシアネート組成物（Ｘ）とポリオール組成物（Ｙ）とが接触した後に、効果的に触媒を作用させる観点から、ポリオール組成物（Ｙ）のみに含まれていることが好ましい。触媒は、二液硬化型接着剤の塗工時に、ポリイソシアネート組成物（Ｘ）および／またはポリオール組成物（Ｙ）に含有させてもよい。 (catalyst)
The two-component curing adhesive of this embodiment may contain a catalyst. The catalyst may be contained in either one of the polyisocyanate composition (X) and the polyol composition (Y), or may be contained in both. The catalyst generally has a high reactivity with the polyisocyanate composition, and after the polyisocyanate composition (X) and the polyol composition (Y) are brought into contact with each other, the catalyst is effectively activated. It is preferably contained only in (Y). The catalyst may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) during coating of the two-component curing adhesive.
　二液硬化型接着剤が触媒を含むことにより、二液硬化型接着剤の硬化が促進され、二液硬化型接着剤を用いて製造した積層フィルムから、芳香族アミンに代表される有害な低分子化学物質が溶出することを抑制できる。すなわち、触媒もポリアミン（Ｃ）等と同様に、硬化促進剤として働く。 When the two-component curing adhesive contains a catalyst, the curing of the two-component curing adhesive is accelerated, and the laminate film produced using the two-component curing adhesive is exposed to harmful low-grade compounds such as aromatic amines. Elution of molecular chemicals can be suppressed. That is, the catalyst also works as a curing accelerator like polyamine (C) and the like.
　触媒としては、ポリイソシアネート組成物（Ｘ）とポリオール組成物（Ｙ）とのウレタン化反応を促進するものであればよく、特に制限はない。触媒としては、例えば、金属系触媒、アミン系触媒、ジアザビシクロウンデセン（ＤＢＵ）、脂肪族環状アミド化合物、チタンキレート錯体等を用いることができる。 The catalyst is not particularly limited as long as it promotes the urethanization reaction between the polyisocyanate composition (X) and the polyol composition (Y). Examples of catalysts that can be used include metal-based catalysts, amine-based catalysts, diazabicycloundecene (DBU), aliphatic cyclic amide compounds, and titanium chelate complexes.
　金属系触媒としては、金属錯体系触媒、無機金属系触媒、有機金属系触媒が挙げられる。
　金属錯体系触媒としては、Ｆｅ（鉄）、Ｍｎ（マンガン）、Ｃｕ（銅）、Ｚｒ（ジルコニウム）、Ｔｈ（トリウム）、Ｔｉ（チタン）、Ａｌ（アルミニウム）及びＣｏ（コバルト）からなる群より選ばれる金属のアセチルアセトナート塩などが挙げられる。具体的には、例えば、鉄アセチルアセトネート、マンガンアセチルアセトネート、銅アセチルアセトネート、ジルコニアアセチルアセトネート等が挙げられる。これらの金属錯体系触媒の中でも、毒性と触媒活性の点から、鉄アセチルアセトネート（Ｆｅ（ａｃａｃ）３）および／又はマンガンアセチルアセトネート（Ｍｎ（ａｃａｃ）２）が好ましい。 Metal-based catalysts include metal complex-based catalysts, inorganic metal-based catalysts, and organic metal-based catalysts.
As the metal complex catalyst, from the group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum) and Co (cobalt) Acetylacetonate salts of selected metals and the like are included. Specific examples include iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, and zirconia acetylacetonate. Among these metal complex catalysts, iron acetylacetonate (Fe(acac) 3 ) and/or manganese acetylacetonate (Mn(acac) 2 ) are preferable from the viewpoint of toxicity and catalytic activity.
　有機金属系触媒としては、スタナスジアセテート、スタナスジオクトエート、スタナスジオレエート、スタナスジラウレート、ジブチル錫オキサイド、ジブチル錫ジアセテート、ジブチル錫ジラウレート、ジブチル錫ジクロライド、ジオクチル錫ジラウレート、オクチル酸ニッケル、ナフテン酸ニッケル、オクチル酸コバルト、ナフテン酸コバルト、オクチル酸ビスマス、ナフテン酸ビスマス、ネオデカン酸ビスマス、ネオデカン酸亜鉛等が挙げられる。これらのうち好ましい有機金属系触媒としては、スタナスジオクトエート、ジブチル錫ジラウレート、ネオデカン酸ビスマス、ネオデカン酸亜鉛もしくはこれらの混合物である。 Organometallic catalysts include stannus diacetate, stannus dioctoate, stannus dioleate, stannus dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, nickel octylate, nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate, bismuth naphthenate, bismuth neodecanoate, zinc neodecanoate and the like. Of these, preferred organometallic catalysts are stannous dioctoate, dibutyltin dilaurate, bismuth neodecanoate, zinc neodecanoate, or mixtures thereof.
　アミン系触媒としては、例えば、トリエチレンジアミン、２－メチルトリエチレンジアミン、キヌクリジン、２－メチルキヌクリジン等が挙げられる。これらの中でも、触媒活性に優れ、工業的に入手可能なことから、アミン系触媒としては、トリエチレンジアミンおよび／または２－メチルトリエチレンジアミンを用いることが好ましい。 Examples of amine-based catalysts include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, and 2-methylquinuclidine. Among these, triethylenediamine and/or 2-methyltriethylenediamine are preferably used as the amine-based catalyst because of their excellent catalytic activity and industrial availability.
　その他の第３級アミン触媒としては、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルプロピレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”－ペンタメチルジエチレントリアミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”－ペンタメチル－（３－アミノプロピル）エチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”－ペンタメチルジプロピレントリアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルヘキサメチレンジアミン、ビス（２－ジメチルアミノエチル）エーテル、ジメチルエタノールアミン、ジメチルイソプロパノールアミン、ジメチルアミノエトキシエタノール、Ｎ，Ｎ－ジメチル－Ｎ’－（２－ヒドロキシエチル）エチレンジアミン、Ｎ，Ｎ－ジメチル－Ｎ’－（２－ヒドロキシエチル）プロパンジアミン、ビス（ジメチルアミノプロピル）アミン、ビス（ジメチルアミノプロピル）イソプロパノールアミン、３－キヌクリジノール、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルグアニジン、１，３，５－トリス（Ｎ，Ｎ－ジメチルアミノプロピル）ヘキサヒドロ－Ｓ－トリアジン、１，８－ジアザビシクロ［５．４．０］ウンデセン－７、Ｎ－メチル－Ｎ’－（２－ジメチルアミノエチル）ピペラジン、Ｎ，Ｎ’－ジメチルピペラジン、ジメチルシクロヘキシルアミン、Ｎ－メチルモルホリン、Ｎ－エチルモルホリン、１－メチルイミダゾール、１，２－ジメチルイミダゾール、１－イソブチル－２－メチルイミダゾール、１－ジメチルアミノプロピルイミダゾール、Ｎ，Ｎ－ジメチルヘキサノールアミン、Ｎ－メチル－Ｎ’－（２－ヒドロキシエチル）ピペラジン、１－（２－ヒドロキシエチル）イミダゾール、１－（２－ヒドロキシプロピル）イミダゾール、１－（２－ヒドロキシエチル）－２－メチルイミダゾール、１－（２－ヒドロキシプロピル）－２－メチルイミダゾール等が挙げられる。 Other tertiary amine catalysts include N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'',N ″-pentamethyldiethylenetriamine, N,N,N′,N″,N″-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N′,N″,N″-pentamethyldipropylenetriamine, N, N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N'-(2-hydroxy ethyl)ethylenediamine, N,N-dimethyl-N'-(2-hydroxyethyl)propanediamine, bis(dimethylaminopropyl)amine, bis(dimethylaminopropyl)isopropanolamine, 3-quinuclidinol, N,N,N', N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 1,8-diazabicyclo[5.4.0]undecene-7, N-methyl-N '-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2 -methylimidazole, 1-dimethylaminopropylimidazole, N,N-dimethylhexanolamine, N-methyl-N'-(2-hydroxyethyl)piperazine, 1-(2-hydroxyethyl)imidazole, 1-(2-hydroxy propyl)imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole and the like.
　触媒として用いられる脂肪族環状アミド化合物としては、例えば、δ－バレロラクタム、ε－カプロラクタム、ω－エナント－ルラクタム、η－カプリルラクタム、β－プロピオラクタム等が挙げられる。これらの脂肪族環状アミド化合物の中でも、ε－カプロラクタムは、二液硬化型接着剤の硬化をより効果的に促進できる。 Examples of aliphatic cyclic amide compounds used as catalysts include δ-valerolactam, ε-caprolactam, ω-enanthrolactam, η-capryllactam and β-propiolactam. Among these aliphatic cyclic amide compounds, ε-caprolactam can more effectively accelerate the curing of two-component curing adhesives.
　本実施形態の二液硬化型接着剤における触媒の含有量は、特に制限はなく、公知の使用量とすることができる。触媒の含有量は、例えば、二液硬化型接着剤の全固形分に対し、０．００１～５．０質量％とすることができる。 The content of the catalyst in the two-component curing adhesive of this embodiment is not particularly limited, and can be a known amount. The content of the catalyst can be, for example, 0.001 to 5.0% by mass with respect to the total solid content of the two-component curing adhesive.
（接着促進剤）
　本実施形態の二液硬化型接着剤は、接着促進剤を含有していてもよい。接着促進剤は、ポリイソシアネート組成物（Ｘ）とポリオール組成物（Ｙ）のいずれか一方にのみ含まれていてもよいし、両方に含まれていてもよい。接着促進剤は、ポリイソシアネート組成物（Ｘ）との反応性が高いため、ポリイソシアネート組成物（Ｘ）とポリオール組成物（Ｙ）とが接触した後に、作用させることが好ましい。このため、接着促進剤は、ポリオール組成物（Ｙ）のみに含まれていることが好ましい。接着促進剤は、二液硬化型接着剤の塗工時に、ポリイソシアネート組成物（Ｘ）および／またはポリオール組成物（Ｙ）に含有させてもよい。
　接着促進剤としては、シランカップリング剤、チタネート系カップチング剤、アルミニウム系等のカップリング剤、エポキシ樹脂などが挙げられる。 (adhesion promoter)
The two-component curing adhesive of this embodiment may contain an adhesion promoter. The adhesion promoter may be contained in either one of the polyisocyanate composition (X) and the polyol composition (Y), or may be contained in both. Since the adhesion promoter has high reactivity with the polyisocyanate composition (X), it is preferred to act after the polyisocyanate composition (X) and the polyol composition (Y) are brought into contact with each other. Therefore, the adhesion promoter is preferably contained only in the polyol composition (Y). The adhesion promoter may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) during coating of the two-component curing adhesive.
Examples of adhesion promoters include silane coupling agents, titanate-based coupling agents, aluminum-based coupling agents, epoxy resins, and the like.
　シランカップリング剤としては、例えば、γ－アミノプロピルトリエトキシシラン、３－グリシジルオキシプロピルトリメトキシシラン、γ－アミノプロピルトリメトキシシラン、Ｎ－β（アミノエチル）－γ－アミノプロピルトリメトキシシラン、Ｎ－β（アミノエチル）－γ－アミノプロピルトリメチルジメトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン等のアミノシラン；β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリエトキシシラン等のエポキシシラン；ビニルトリス（β－メトキシエトキシ）シラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、γ－メタクリロキシプロピルトリメトキシシラン等のビニルシラン；ヘキサメチルジシラザン、γ－メルカプトプロピルトリメトキシシラン等を挙げることが出来る。 Silane coupling agents include, for example, γ-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, Aminosilanes such as N-β(aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycides epoxysilanes such as xypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane; vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane; ; hexamethyldisilazane, γ-mercaptopropyltrimethoxysilane, and the like.
　チタネート系カップリング剤としては、例えば、テトライソプロポキシチタン、テトラ－ｎ－ブトキシチタン、ブチルチタネートダイマー、テトラステアリルチタネート、チタンアセチルアセトネート、チタンラクテート、テトラオクチレングリコールチタネート、チタンラクテート、テトラステアロキシチタン等を挙げることが出来る。
　アルミニウム系カップリング剤としては、例えば、アセトアルコキシアルミニウムジイソプロピレート等が挙げることが出来る。 Titanate-based coupling agents include, for example, tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, tetrastearoxy Titanium etc. can be mentioned.
Examples of aluminum-based coupling agents include acetoalkoxyaluminum diisopropylate.
　エポキシ樹脂としては、一般的に市販されているエピ－ビス型、ノボラック型、β－メチルエピクロ型、環状オキシラン型、グリシジルエーテル型、グリシジルエステル型、ポリグリコールエーテル型、グリコールエーテル型、エポキシ化脂肪酸エステル型、多価カルボン酸エステル型、アミノグリシジル型、レゾルシン型等の各種エポキシ樹脂が挙げられる。 As the epoxy resin, generally commercially available epi-bis type, novolac type, β-methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, polyvalent carboxylic acid ester type, aminoglycidyl type, resorcinol type, and other epoxy resins.
　本実施形態の二液硬化型接着剤における接着促進剤の含有量は、特に制限はなく、公知の使用量とすることができる。接着促進剤の含有量は、例えば、二液硬化型接着剤の全固形分に対し、０～５０質量％とすることができる。 The content of the adhesion promoter in the two-component curing adhesive of this embodiment is not particularly limited, and can be a known amount. The content of the adhesion promoter can be, for example, 0 to 50% by mass with respect to the total solid content of the two-component curing adhesive.
（顔料）
　本実施形態の二液硬化型接着剤は、必要に応じて、顔料を併用してもよい。顔料は、ポリイソシアネート組成物（Ｘ）とポリオール組成物（Ｙ）のいずれか一方にのみ含まれていてもよいし、両方に含まれていてもよい。顔料は、二液硬化型接着剤の塗工時に、ポリイソシアネート組成物（Ｘ）および／またはポリオール組成物（Ｙ）に含有させてもよい。 (pigment)
The two-component curing adhesive of the present embodiment may be used in combination with a pigment, if necessary. The pigment may be contained in either one of the polyisocyanate composition (X) and the polyol composition (Y), or may be contained in both. The pigment may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) during coating of the two-component curing adhesive.
　顔料としては、特に限定されるものではなく、種々のものが掲げられる。顔料としては、例えば、塗料原料便覧１９７０年度版（日本塗料工業会編）に記載されている体質顔料、白顔料、黒顔料、灰色顔料、赤色顔料、茶色顔料、緑色顔料、青顔料、金属粉顔料、発光顔料、真珠色顔料等の有機顔料、無機顔料、プラスチック顔料などが挙げられる。 The pigment is not particularly limited, and includes various pigments. Examples of pigments include extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, and metal powders described in the 1970 edition of Handbook of Paint Materials (edited by the Japan Paint Manufacturers Association). Examples include organic pigments such as pigments, luminescent pigments and pearlescent pigments, inorganic pigments, and plastic pigments.
　有機顔料としては、例えば、ベンチジンエロー、ハンザエロー、レーキッド４Ｒ等の各種の不溶性アゾ顔料；レーキッドＣ、カーミン６Ｂ、ボルドー１０等の溶性アゾ顔料；フタロシアニンブルー、フタロシアニングリーン等の各種（銅）フタロシアニン系顔料；ローダミンレーキ、メチルバイオレットレーキ等の各種の塩素性染め付けレーキ；キノリンレーキ、ファストスカイブルー等の各種の媒染染料系顔料；アンスラキノン系顔料、チオインジゴ系顔料、ペリノン系顔料等の各種の建染染料系顔料；シンカシアレッドＢ等の各種のキナクリドン系顔料；ヂオキサジンバイオレット等の各種のヂオキサジン系顔料；クロモフタール等の各種の縮合アゾ顔料；アニリンブラックなどが挙げられる。 Examples of organic pigments include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow and Laked 4R; soluble azo pigments such as Laked C, Carmine 6B and Bordeaux 10; various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green. Pigments; various chlorine dyeing lakes such as rhodamine lake and methyl violet lake; various mordant pigments such as quinoline lake and fast sky blue; various vat dyes such as anthraquinone pigments, thioindigo pigments and perinone pigments dye-based pigments; various quinacridone-based pigments such as Cincasia Red B; various dioxazine-based pigments such as dioxazine violet; various condensed azo pigments such as chromophtal;
　無機顔料としては、例えば、黄鉛、ジンククロメート、モリブデートオレンジ等の如き、各種のクロム酸塩；紺青等の各種のフェロシアン化合物；酸化チタン、亜鉛華、マピコエロー、酸化鉄、ベンガラ、酸化クロームグリーン、酸化ジルコニウム等の各種の金属酸化物；カドミウムエロー、カドミウムレッド、硫化水銀等の各種の硫化物ないしはセレン化物；硫酸バリウム、硫酸鉛等の各種の硫酸塩；ケイ酸カルシウム、群青等の各種のケイ酸塩；炭酸カルシウム、炭酸マグネシウム等の各種の炭酸塩；コバルトバイオレット、マンガン紫等の各種の燐酸塩；アルミニウム粉、金粉、銀粉、銅粉、ブロンズ粉、真鍮粉等の各種の金属粉末顔料；これら金属のフレーク顔料、マイカ・フレーク顔料；金属酸化物を被覆した形のマイカ・フレーク顔料、雲母状酸化鉄顔料等のメタリック顔料やパール顔料；黒鉛、カーボンブラック等が挙げられる。 Examples of inorganic pigments include various chromates such as yellow lead, zinc chromate, and molybdate orange; various ferrocyanic compounds such as Prussian blue; titanium oxide, zinc white, mapico yellow, iron oxide, red iron oxide, and chromium oxide. various metal oxides such as green and zirconium oxide; various sulfides and selenides such as cadmium yellow, cadmium red, and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various types such as calcium silicate and ultramarine blue various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powders such as aluminum powder, gold powder, silver powder, copper powder, bronze powder and brass powder. pigments; flake pigments of these metals, mica flake pigments; metallic pigments and pearl pigments such as mica flake pigments coated with metal oxides and mica-like iron oxide pigments; graphite, carbon black and the like.
　体質顔料としては、例えば、沈降性硫酸バリウム、ご粉、沈降炭酸カルシウム、重炭酸カルシウム、寒水石、アルミナ白、シリカ、含水微粉シリカ（ホワイトカーボン）、超微粉無水シリカ（アエロジル）、珪砂（シリカサンド）、タルク、沈降性炭酸マグネシウム、ベントナイト、クレー、カオリン、黄土などが挙げられる。
　プラスチック顔料としては、例えば、ＤＩＣ株式会社製の「グランドールＰＰ－１０００」、「ＰＰ－２０００Ｓ」等が挙げられる。 Extender pigments include, for example, precipitated barium sulfate, rice flour, precipitated calcium carbonate, calcium bicarbonate, Kansui stone, alumina white, silica, hydrous fine silica (white carbon), ultrafine anhydrous silica (Aerosil), silica sand (silica sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess, and the like.
Examples of plastic pigments include "Glandole PP-1000" and "PP-2000S" manufactured by DIC Corporation.
　顔料としては、耐久性、耐侯性、意匠性に優れることから、白色顔料としての酸化チタン、亜鉛華等の無機酸化物、黒色顔料としてのカーボンブラックを用いることがより好ましい。 As the pigment, it is more preferable to use inorganic oxides such as titanium oxide and zinc oxide as white pigments, and carbon black as black pigments, since they are excellent in durability, weather resistance, and design.
　本実施形態の二液硬化型接着剤における顔料の含有量は、ポリイソシアネート組成物（Ｘ）とポリオール組成物（Ｙ）の全固形分合計１００質量部に対して、１～４００質量部とすることが好ましく、１０～３００質量部とすることがより好ましい。顔料の含有量が、１～４００質量部であると、接着性、耐ブロッキング性に優れる二液硬化型接着剤となる。 The content of the pigment in the two-component curing adhesive of the present embodiment is 1 to 400 parts by mass with respect to 100 parts by mass of the total solid content of the polyisocyanate composition (X) and the polyol composition (Y). is preferred, and 10 to 300 parts by mass is more preferred. When the content of the pigment is 1 to 400 parts by mass, a two-part curing adhesive having excellent adhesion and anti-blocking properties can be obtained.
（添加剤）
　本発明の二液硬化型接着剤は、必要であれば、上述した成分以外にその他の添加剤を含有していてもよい。添加剤は、ポリイソシアネート組成物（Ｘ）とポリオール組成物（Ｙ）のいずれか一方にのみ含まれていてもよいし、両方に含まれていてもよい。添加剤は、二液硬化型接着剤の塗工時に、ポリイソシアネート組成物（Ｘ）および／またはポリオール組成物（Ｙ）に含有させてもよい。 (Additive)
The two-component curing adhesive of the present invention may contain other additives in addition to the components described above, if necessary. The additive may be contained in either one of the polyisocyanate composition (X) and the polyol composition (Y), or may be contained in both. The additive may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) during coating of the two-component curing adhesive.
　添加剤としては、例えば、レベリング剤；コロイド状シリカ、アルミナゾルなどの無機微粒子；ポリメチルメタクリレート系の有機微粒子；消泡剤；タレ性防止剤；湿潤分散剤；粘性調整剤；紫外線吸収剤；金属不活性化剤；過酸化物分解剤；難燃剤；補強剤；可塑剤；潤滑剤；防錆剤；蛍光性増白剤；無機系熱線吸収剤；防炎剤；帯電防止剤；脱水剤などが挙げられる。 Additives include, for example, leveling agents; inorganic fine particles such as colloidal silica and alumina sol; polymethylmethacrylate-based organic fine particles; antifoaming agents; Deactivator; peroxide decomposer; flame retardant; reinforcing agent; plasticizer; lubricant; rust inhibitor; fluorescent whitening agent; is mentioned.
　本実施形態の二液硬化型接着剤は、ポリイソシアネート組成物（Ｘ）とポリオール組成物（Ｙ）との硬化反応を用いる二液硬化型接着剤であって、ポリイソシアネート組成物（Ｘ）がポリイソシアネート（Ａ）を含み、ポリオール組成物（Ｙ）がポリオール（Ｂ）を含み、ポリイソシアネート組成物（Ｘ）およびポリオール組成物（Ｙ）の伸長粘度が０．１～１０Ｐａ・ｓである。 The two-component curable adhesive of the present embodiment is a two-component curable adhesive using a curing reaction between the polyisocyanate composition (X) and the polyol composition (Y), wherein the polyisocyanate composition (X) is It contains polyisocyanate (A), polyol composition (Y) contains polyol (B), and extensional viscosity of polyisocyanate composition (X) and polyol composition (Y) is 0.1 to 10 Pa·s.
　このため、本実施形態の二液硬化型接着剤は、二液分別塗布工程を有する製造方法により積層フィルムを製造する場合に、第一フィルム上に塗布されたポリイソシアネート組成物（Ｘ）と、第二フィルム上に塗布されたポリオール組成物（Ｙ）とを接触させる工程においてミスティングが発生しにくく、且つ、初期凝集力にも優れる。
　このため、本実施形態の二液硬化型接着剤は、例えば、二液混合塗布工程を有する製造方法、二液分別塗布工程を有する製造方法などの製造方法を用いて、積層フィルムを製造する場合に好適に用いることができる。 For this reason, the two-component curing adhesive of the present embodiment can be used in the case of producing a laminated film by a production method having a two-component separate application step, the polyisocyanate composition (X) applied on the first film, In the step of contacting the polyol composition (Y) coated on the second film, misting is less likely to occur, and the initial cohesion is also excellent.
For this reason, the two-component curable adhesive of the present embodiment can be used, for example, when manufacturing a laminated film using a manufacturing method including a two-component mixed coating process and a manufacturing method including a two-component separate coating process. It can be suitably used for
　特に、従来、二液分別塗布工程を有する方法を用いて積層フィルムを製造する場合には、ミスティングが発生しやすかった。本実施形態の二液硬化型接着剤によれば、ポリイソシアネート組成物（Ｘ）およびポリオール組成物（Ｙ）の伸長粘度が０．１～１０Ｐａ・ｓであることにより、ミスティングの発生を抑制できる。また、二液分別塗布工程を有する方法では、初期凝集力が不足する場合があるが、ポリイソシアネート組成物（Ｘ）およびポリオール組成物（Ｙ）の伸長粘度が０．１～１０Ｐａ・ｓであることにより、初期凝集力の問題を解決することが可能となる。
　このため、本実施形態の二液硬化型接着剤は、二液分別塗布工程を有する方法を用いて積層フィルムを製造する場合に、特に好適に用いることができる。 In particular, conventionally, when a laminated film is produced using a method having a two-liquid separate coating process, misting tends to occur. According to the two-component curing adhesive of the present embodiment, the elongational viscosity of the polyisocyanate composition (X) and the polyol composition (Y) is 0.1 to 10 Pa s, thereby suppressing the occurrence of misting. can. In addition, in the method having a two-part separate coating process, the initial cohesive force may be insufficient, but the extensional viscosity of the polyisocyanate composition (X) and the polyol composition (Y) is 0.1 to 10 Pa s. This makes it possible to solve the problem of initial cohesion.
For this reason, the two-component curing adhesive of the present embodiment can be used particularly suitably when manufacturing a laminated film using a method having a two-component separate coating process.
　本実施形態の二液硬化型接着剤は、ポリイソシアネート組成物（Ｘ）およびポリオール組成物（Ｙ）の伸長粘度が０．１～１０Ｐａ・ｓである。本実施形態の二液硬化型接着剤は、ポリオール組成物（Ｙ）とポリイソシアネート組成物（Ｘ）との反応性が良好である。したがって、エージング温度を低くしたり、エージング時間を短縮したりできる。 In the two-component curing adhesive of the present embodiment, the elongational viscosity of the polyisocyanate composition (X) and the polyol composition (Y) is 0.1 to 10 Pa·s. The two-component curing adhesive of the present embodiment has good reactivity between the polyol composition (Y) and the polyisocyanate composition (X). Therefore, the aging temperature can be lowered and the aging time can be shortened.
［積層フィルム］
　次に、本実施形態の積層フィルムについて、図面を用いて詳細に説明する。
　図１は、本実施形態に係る積層フィルムの一例を示した断面図である。図１に示すように、本実施形態の積層フィルム１１ａは、第一フィルムＷ１と第二フィルムＷ２との間に接着剤層１０を有する。本実施形態の積層フィルム１１ａにおいては、接着剤層１０が上記実施形態の二液硬化型接着剤の硬化物からなる。 [Laminated film]
Next, the laminated film of this embodiment will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view showing an example of the laminated film according to this embodiment. As shown in FIG. 1, the laminated film 11a of this embodiment has an adhesive layer 10 between the first film W1 and the second film W2. In the laminated film 11a of the present embodiment, the adhesive layer 10 is made of the cured two-component curing adhesive of the above embodiment.
（フィルム）
　本実施形態の積層フィルム１１ａにおいて、第一フィルムＷ１および第二フィルムＷ２として使用するフィルムには、公知の積層フィルムに使用されるプラスチックフィルムを用いることが好ましい。
　第一フィルムＷ１としては、例えば、ポリエチレンテレフタラート（以下「ＰＥＴ」と略記する場合がある。）フィルム、ナイロン（ＯＰＡ）フィルム、２軸延伸ポリプロピレン（ＯＰＰ）フィルム、各種蒸着フィルム等のベースフィルム、アルミ箔等を用いることができる。
　第二フィルムＷ２としては、例えば、無延伸ポリプロピレン（ＣＰＰ）フィルム、直鎖低密度ポリエチレン（ＬＬＤＰＥ）フィルム等のシーラントフィルムを用いることができる。 (the film)
In the laminated film 11a of the present embodiment, it is preferable to use plastic films used for known laminated films for the films used as the first film W1 and the second film W2.
Examples of the first film W1 include base films such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") film, nylon (OPA) film, biaxially oriented polypropylene (OPP) film, various vapor deposition films, Aluminum foil or the like can be used.
As the second film W2, for example, a sealant film such as an unstretched polypropylene (CPP) film or a linear low density polyethylene (LLDPE) film can be used.
　第一フィルムＷ１および第二フィルムＷ２としては、天然紙、合成紙、コーティング紙などの紙を使用してもよい。
　第一フィルムＷ１および／または第二フィルムＷ２の外表面または内面側には、必要に応じて印刷層を設けてもよい。 Paper such as natural paper, synthetic paper, and coated paper may be used as the first film W1 and the second film W2.
A printed layer may be provided on the outer surface or inner surface side of the first film W1 and/or the second film W2, if necessary.
　本実施形態の積層フィルム１１ａは、軟包装フィルム、軟包装（包装の形が内容物を入れることにより形作られるような包装）材料、洗剤、薬剤、食品、飲料等を充填する包装材料などとして工業的に使用できる。洗剤、薬剤としては、具体的には例えば、洗濯用液体洗剤、台所用液体洗剤、浴用液体洗剤、浴用液体石鹸、液体シャンプー、液体コンディショナー等が挙げられる。食品、飲料としては特に限定されるものではない。
　本実施形態の積層フィルム１１ａは、袋状に成形することにより、包装体として使用できる。 The laminated film 11a of the present embodiment is industrially used as a flexible packaging film, a flexible packaging (package whose shape is formed by putting contents in it) material, a packaging material for filling detergents, medicines, foods, beverages, etc. can be used as intended. Specific examples of detergents and chemicals include liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, and liquid conditioners. Foods and beverages are not particularly limited.
The laminated film 11a of this embodiment can be used as a package by forming it into a bag shape.
　本実施形態の積層フィルム１１ａは、第一フィルムＷ１と第二フィルムＷ２との間に接着剤層１０を有し、接着剤層１０が、上記実施形態の二液硬化型接着剤の硬化物からなる。このため、本実施形態の積層フィルム１１ａは、初期凝集力に優れ、フィルム上に塗布する工程を行ってもミスティングが発生しにくい、上記実施形態の二液硬化型接着剤を用いて製造できる。よって、本実施形態の積層フィルムは、例えば、二液混合塗布工程を有する製造方法、二液分別塗布工程を有する製造方法などの製造方法を用いて、効率よく製造できる。さらに、上記実施形態の二液硬化型接着剤が、短時間および／または低温で硬化するものであるため、本実施形態の積層フィルム１１ａは、少ないエネルギー量で製造できる。 The laminated film 11a of the present embodiment has an adhesive layer 10 between the first film W1 and the second film W2, and the adhesive layer 10 is formed from the cured two-component curable adhesive of the above embodiment. Become. Therefore, the laminated film 11a of the present embodiment can be manufactured using the two-component curable adhesive of the above embodiment, which has excellent initial cohesive strength and is less prone to misting even when the step of applying it onto the film is performed. . Therefore, the laminated film of the present embodiment can be efficiently manufactured using a manufacturing method such as a manufacturing method including a two-component mixed coating process and a manufacturing method including a two-component separate coating process. Furthermore, since the two-component curing adhesive of the above embodiment cures in a short time and/or at a low temperature, the laminated film 11a of this embodiment can be produced with a small amount of energy.
［積層フィルム製造装置］
　次に、図面を参照しつつ、本実施形態の積層フィルム１１ａの製造装置について詳細に説明する。
　図２は、本実施形態に係る積層フィルムの製造装置の正面図である。図３は、図２に示す積層フィルムの製造装置におけるポリイソシアネート塗工部の要部を示す正面図である。図４は、図２に示す積層フィルムの製造装置におけるポリオール塗工部の要部を示す正面図である。 [Laminated film manufacturing equipment]
Next, the manufacturing apparatus for the laminated film 11a of this embodiment will be described in detail with reference to the drawings.
FIG. 2 is a front view of the laminated film manufacturing apparatus according to the present embodiment. 3 is a front view showing a main part of a polyisocyanate coating section in the laminated film manufacturing apparatus shown in FIG. 2. FIG. 4 is a front view showing a main part of a polyol coating section in the laminated film manufacturing apparatus shown in FIG. 2. FIG.
　図２に示す積層フィルムの製造装置１は、上述した本実施形態の二液硬化型接着剤を用いて、ロールから巻き出した第一フィルムＷ１とロールから巻き出したの第二フィルムＷ２とを貼り合わせて、第一フィルムＷ１と第二フィルムＷ２との間に接着剤層１０を形成し、ロール状に巻き取られた上述した本実施形態の積層フィルム１１ａを製造する装置である。 The laminated film manufacturing apparatus 1 shown in FIG. 2 uses the two-component curing adhesive of the present embodiment described above to separate the first film W1 unwound from the roll and the second film W2 unwound from the roll. This apparatus forms the adhesive layer 10 between the first film W1 and the second film W2 by sticking them together, and manufactures the above-described laminated film 11a of the present embodiment wound into a roll.
　本実施形態の積層フィルムの製造装置１は、図２に示すように、第１巻出部１１と、ポリイソシアネート塗工部１２（第一塗工部）と、第２巻出部１３と、ポリオール塗工部１４（第二塗工部）と、貼合装置１５とを備える。
　第１巻出部１１は、第一フィルムＷ１をポリイソシアネート塗工部１２へ送出する。第一フィルムＷ１は、第１巻出部１１のフィルム装着部１１１に回転可能に装着されている。 As shown in FIG. 2, the laminated film manufacturing apparatus 1 of the present embodiment includes a first unwinding section 11, a polyisocyanate coating section 12 (first coating section), a second unwinding section 13, A polyol coating unit 14 (second coating unit) and a bonding device 15 are provided.
The first unwinding section 11 delivers the first film W1 to the polyisocyanate coating section 12 . The first film W1 is rotatably mounted on the film mounting portion 111 of the first unwinding portion 11 .
　ポリイソシアネート塗工部１２は、第１巻出部１１から送出された第一フィルムＷ１に、本実施形態の二液硬化型接着剤のポリイソシアネート組成物（Ｘ）を塗布する。
　ポリイソシアネート塗工部１２は、図３に示すように、４本スクイズロール方式のロールコーターである。ポリイソシアネート塗工部１２は、アプリケーションロール１２１と、ドクターロール１２２と、メタリングロール１２３と、コーティングロール１２４と、バッキングロール１２５とを備える。アプリケーションロール１２１とドクターロール１２２との対向部分には、液溜部１２０が備えられている。 The polyisocyanate coating section 12 applies the polyisocyanate composition (X) of the two-component curing adhesive of the present embodiment to the first film W1 delivered from the first unwinding section 11 .
As shown in FIG. 3, the polyisocyanate coating section 12 is a four-roll squeeze roll coater. The polyisocyanate coating section 12 includes an application roll 121 , a doctor roll 122 , a metering roll 123 , a coating roll 124 and a backing roll 125 . A liquid reservoir 120 is provided at a portion where the application roll 121 and the doctor roll 122 face each other.
　アプリケーションロール１２１は、ゴム等の弾性素材の外周面を備えるロールである。ドクターロール１２２は、金属（非弾性素材）の外周面を備えるロールである。図３に示すように、アプリケーションロール１２１及びドクターロール１２２は、回転軸が互いに平行となるように、ポリイソシアネート塗工部１２に回転可能に支持されている。アプリケーションロール１２１の外周面とドクターロール１２２の外周面とは、微小間隔をもって対向している。 The application roll 121 is a roll having an outer peripheral surface made of an elastic material such as rubber. The doctor roll 122 is a roll having an outer peripheral surface made of metal (inelastic material). As shown in FIG. 3, the application roll 121 and the doctor roll 122 are rotatably supported by the polyisocyanate coating section 12 so that their rotation axes are parallel to each other. The outer peripheral surface of the application roll 121 and the outer peripheral surface of the doctor roll 122 face each other with a minute gap therebetween.
　アプリケーションロール１２１とドクターロール１２２との対向部分の上部には、アプリケーションロール１２１およびドクターロール１２２の回転軸方向に、所定の間隔で一対の堰板１２６が設置されている。一対の堰板１２６と、アプリケーションロール１２１の外周面と、ドクターロール１２２の外周面とによって、液溜部１２０が形成されている。
　液溜部１２０は、ポリイソシアネート組成物（Ｘ）を一時的に貯留する。ポリイソシアネート組成物（Ｘ）は、図示しないポリイソシアネート供給部から液溜部１２０へ供給される。これにより、液溜部１２０に貯留されているポリイソシアネート組成物（Ｘ）は、一定量に保持されている。 A pair of barrier plates 126 is installed at a predetermined interval in the direction of the rotation axis of the application roll 121 and the doctor roll 122 above the portion where the application roll 121 and the doctor roll 122 face each other. A liquid reservoir 120 is formed by the pair of barrier plates 126 , the outer peripheral surface of the application roll 121 , and the outer peripheral surface of the doctor roll 122 .
The liquid reservoir 120 temporarily stores the polyisocyanate composition (X). The polyisocyanate composition (X) is supplied to the liquid reservoir 120 from a polyisocyanate supply section (not shown). Thereby, the polyisocyanate composition (X) stored in the liquid reservoir 120 is held at a constant amount.
　ドクターロール１２２は、図示しない温度調節部を備えることが好ましい。温度調節部は、液溜部１２０に貯留されているポリイソシアネート組成物（Ｘ）を一定の温度に保ち、ポリイソシアネート組成物（Ｘ）の粘度を安定化する。これにより、ドクターロール１２２の外周面は、一定の温度に保たれている。
　図３に示すように、アプリケーションロール１２１、ドクターロール１２２は、液溜部１２０で下向きに回転する。このことにより、ドクターロール１２２の外周面に、微小隙間を通過したポリイソシアネート組成物（Ｘ）が塗布される。 The doctor roll 122 preferably has a temperature control section (not shown). The temperature control section keeps the polyisocyanate composition (X) stored in the liquid reservoir section 120 at a constant temperature and stabilizes the viscosity of the polyisocyanate composition (X). Thereby, the outer peripheral surface of the doctor roll 122 is kept at a constant temperature.
As shown in FIG. 3, the application roll 121 and doctor roll 122 rotate downward in the liquid reservoir 120 . As a result, the outer peripheral surface of the doctor roll 122 is coated with the polyisocyanate composition (X) that has passed through the minute gaps.
　図３に示すように、ポリイソシアネート塗工部１２は、メタリングロール１２３、コーティングロール１２４、バッキングロール１２５を回転可能に支持している。
　メタリングロール１２３には、ドクターロール１２２の外周面に塗布されたポリイソシアネート組成物（Ｘ）が転写される。メタリングロール１２３の回転軸は、ドクターロール１２２の回転軸と平行に配置されている。メタリングロール１２３の外周面は、ゴム等の弾性素材で形成されている。メタリングロール１２３の外周面は、ドクターロール１２２の外周面に圧接されている。 As shown in FIG. 3, the polyisocyanate coating section 12 rotatably supports a metering roll 123, a coating roll 124, and a backing roll 125. As shown in FIG.
The polyisocyanate composition (X) applied to the outer peripheral surface of the doctor roll 122 is transferred to the metering roll 123 . The rotating shaft of the metering roll 123 is arranged parallel to the rotating shaft of the doctor roll 122 . The outer peripheral surface of the metering roll 123 is made of an elastic material such as rubber. The outer peripheral surface of the metering roll 123 is pressed against the outer peripheral surface of the doctor roll 122 .
　コーティングロール１２４には、メタリングロール１２３の外周面に塗布されたポリイソシアネート組成物（Ｘ）が転写される。コーティングロール１２４の回転軸は、メタリングロール１２３の回転軸と平行に配置されている。また、コーティングロール１２４の外周面は、金属素材で形成されている。コーティングロール１２４の外周面は、メタリングロール１２３の外周面に圧接されている。 The polyisocyanate composition (X) applied to the outer peripheral surface of the metering roll 123 is transferred to the coating roll 124 . The rotation axis of the coating roll 124 is arranged parallel to the rotation axis of the metering roll 123 . Moreover, the outer peripheral surface of the coating roll 124 is formed of a metal material. The outer peripheral surface of the coating roll 124 is pressed against the outer peripheral surface of the metering roll 123 .
　バッキングロール１２５は、コーティングロール１２４と回転軸同士が平行となるように、配置されている。バッキングロール１２５は、コーティングロール１２４との間で第二フィルムＷ２を挟持し、第二フィルムＷ２を搬送する。バッキングロール１２５は、コーティングロール１２４の外周面に塗布されたポリイソシアネート組成物（Ｘ）の第一フィルムＷ１への転写を補助する。バッキングロール１２５の外周面は、ゴム等の弾性素材で形成されている。
　コーティングロール１２４は、ドクターロール１２２と同様に、図示しない温度調節部によって外周面の温度が一定に保たれていることが好ましい。これにより、第一フィルムＷ１に塗布されるポリイソシアネート組成物（Ｘ）の粘度が安定化される。 The backing roll 125 is arranged so that the rotating shafts of the coating roll 124 are parallel to each other. The backing roll 125 sandwiches the second film W2 between itself and the coating roll 124, and conveys the second film W2. The backing roll 125 assists the transfer of the polyisocyanate composition (X) applied to the outer peripheral surface of the coating roll 124 to the first film W1. The outer peripheral surface of the backing roll 125 is made of an elastic material such as rubber.
Like the doctor roll 122, the coating roll 124 preferably has a constant temperature of the outer peripheral surface by a temperature control unit (not shown). This stabilizes the viscosity of the polyisocyanate composition (X) applied to the first film W1.
　一般的にミスティングは、ポリイソシアネート組成物（Ｘ）がロール間を転写により移動する際に発生する。通常、ミスティングが発生しうる箇所としては、例えば、ドクターロール１２２とメタリングロール１２３とが圧接された付近、メタリングロール１２３とコーティングロール１２４とが圧接された付近、コーティングロール１２４とバッキングロール１２５とが圧接された付近が挙げられる。ミスティングが発生する場合には、ミスティングの発生を抑えるために、各ロールの回転速度および第一フィルムＷ１の搬送速度を下げる必要がある。しかし、第一フィルムＷ１の搬送速度を下げると、積層フィルム１１ａの生産効率が低下する。 Generally, misting occurs when the polyisocyanate composition (X) moves between rolls due to transfer. Locations where misting usually occurs include, for example, the area where the doctor roll 122 and the metering roll 123 are in pressure contact, the area where the metering roll 123 and the coating roll 124 are in pressure contact, and the coating roll 124 and the backing roll. The vicinity where 125 is press-contacted can be mentioned. When misting occurs, it is necessary to reduce the rotation speed of each roll and the transport speed of the first film W1 in order to suppress the occurrence of misting. However, when the conveying speed of the first film W1 is lowered, the production efficiency of the laminated film 11a is lowered.
　本実施形態では、ポリイソシアネート組成物（Ｘ）として、特定の伸長粘度を有する組成物を用いることにより、ミスティングの発生を抑制できる。その結果、優れた特性を有する積層フィルム１１ａを効率よく製造できる。本実施態様の様に、ロールコーターを用いてポリイソシアネート組成物（Ｘ）の塗布を行う場合には、ミスティングが発生しうる箇所が多くなる。したがって、ポリイソシアネート組成物（Ｘ）の伸長粘度を厳密に制御することによる効果が、より顕著となる。 In the present embodiment, misting can be suppressed by using a composition having a specific elongational viscosity as the polyisocyanate composition (X). As a result, the laminated film 11a having excellent properties can be efficiently produced. When the polyisocyanate composition (X) is applied using a roll coater as in this embodiment, there are many locations where misting may occur. Therefore, the effect of strictly controlling the elongational viscosity of the polyisocyanate composition (X) becomes more pronounced.
　第２巻出部１３は、第二フィルムＷ２をポリオール塗工部１４へ送出する。第二フィルムＷ２は、第２巻出部１３のフィルム装着部１３１に回転可能に装着されている。
　ポリオール塗工部１４は、第２巻出部１３から送出された第二フィルムＷ２に、本実施形態の二液硬化型接着剤のポリオール組成物（Ｙ）を塗布する。
　ポリオール塗工部１４は、図４に示すように、ポリオール組成物（Ｙ）をグラビア印刷で塗布するグラビア塗工機（グラビアコーター）である。ポリオール塗工部１４は、グラビアロール１４１、チャンバー１４２、圧胴１４３、塗工液タンク１４４、ポンプ１４５、温度調節機１４６を備える。 The second unwinding section 13 delivers the second film W2 to the polyol coating section 14 . The second film W2 is rotatably mounted on the film mounting portion 131 of the second unwinding portion 13 .
The polyol coating section 14 applies the polyol composition (Y) of the two-component curing adhesive of the present embodiment to the second film W2 delivered from the second unwinding section 13 .
The polyol coating unit 14, as shown in FIG. 4, is a gravure coating machine (gravure coater) that applies the polyol composition (Y) by gravure printing. The polyol coating section 14 includes a gravure roll 141 , a chamber 142 , an impression cylinder 143 , a coating liquid tank 144 , a pump 145 and a temperature controller 146 .
　グラビアロール１４１は、ポリオール塗工部１４に回転可能に支持された金属製のロールである。グラビアロール１４１の表面には、例えば、レーザー彫刻により、複数の凹部（グラビアパターン）が形成されている。凹部の容積、開口比、深さ等を変化させることにより、グラビアロール１４１の表面に塗布される塗工液の量を調整できる。グラビアロール１４１の表面に施されるグラビアパターンは、特に限定されるものではなく、例えば、ハニカムパターンとすることができる。 The gravure roll 141 is a metal roll rotatably supported by the polyol coating section 14 . A plurality of recesses (gravure pattern) are formed on the surface of the gravure roll 141 by, for example, laser engraving. By changing the volume, opening ratio, depth, etc. of the recesses, the amount of the coating liquid applied to the surface of the gravure roll 141 can be adjusted. The gravure pattern applied to the surface of the gravure roll 141 is not particularly limited, and may be, for example, a honeycomb pattern.
　図４に示すように、チャンバー１４２は、ポリオール組成物（Ｙ）を貯留する容器である。チャンバー１４２は、グラビアロール１４１の径方向の一側方に配置されている。
　チャンバー１４２は、ポリオール組成物（Ｙ）を貯留する貯留部１４２ａを備える。貯留部１４２ａは、グラビアロール１４１側に開口している。グラビアロール１４１の外周面の一部は、貯留部１４２ａ内に貯留されたポリオール組成物（Ｙ）に浸されている。
　貯留部１４２ａは、ドクターブレード１４２ｂ、シールプレート１４２ｃ、１対のサイドプレート１４２ｄによって密閉されている。 As shown in FIG. 4, the chamber 142 is a container that stores the polyol composition (Y). The chamber 142 is arranged on one radial side of the gravure roll 141 .
The chamber 142 has a storage part 142a that stores the polyol composition (Y). The storage part 142a is open to the gravure roll 141 side. A part of the outer peripheral surface of the gravure roll 141 is immersed in the polyol composition (Y) stored in the storage part 142a.
The reservoir 142a is sealed by a doctor blade 142b, a seal plate 142c and a pair of side plates 142d.
　チャンバー１４２は、板状のドクターブレード１４２ｂを備える。ドクターブレード１４２ｂは、貯留部１４２ａの開口上端部からグラビアロール１４１に向けて突設されている。ドクターブレード１４２ｂの材質は、特に限定されず、金属でもよいし、樹脂でもよく、例えば、ステンレスからなるものとすることができる。
　ドクターブレード１４２ｂの先端部は、グラビアロール１４１の外周面に圧接されている。ドクターブレード１４２ｂの先端部は、貯留部１４２ａのロール回転方向下流側をシールする。ドクターブレード１４２ｂは、グラビアロール１４１の外周面に付着する余分なポリオール組成物（Ｙ）を、グラビアロール１４１の回転動作により掻き取って計量する。 The chamber 142 has a plate-like doctor blade 142b. The doctor blade 142b protrudes toward the gravure roll 141 from the upper end of the opening of the reservoir 142a. The material of the doctor blade 142b is not particularly limited, and may be metal or resin, for example, stainless steel.
The tip of the doctor blade 142 b is pressed against the outer peripheral surface of the gravure roll 141 . The tip of the doctor blade 142b seals the downstream side of the reservoir 142a in the roll rotation direction. The doctor blade 142b scrapes off excess polyol composition (Y) adhering to the outer peripheral surface of the gravure roll 141 by rotating the gravure roll 141 and weighs it.
　チャンバー１４２は、板状のシールプレート１４２ｃを備える。シールプレート１４２ｃは、樹脂製である。シールプレート１４２ｃは、貯留部１４２ａの開口下端部からグラビアロール１４１に向けて突設されている。
　シールプレート１４２ｃの先端部は、グラビアロール１４１の外周面に圧接されている。シールプレート１４２ｃの先端部は、貯留部１４２ａのロール回転方向上流側をシールする。 The chamber 142 has a plate-like seal plate 142c. The seal plate 142c is made of resin. The seal plate 142c protrudes toward the gravure roll 141 from the lower end of the opening of the reservoir 142a.
The tip of the seal plate 142 c is pressed against the outer peripheral surface of the gravure roll 141 . The tip of the seal plate 142c seals the upstream side of the reservoir 142a in the roll rotation direction.
　チャンバー１４２は、樹脂製のサイドプレート１４２ｄを備える。サイドプレート１４２ｄは、チャンバー１４２の両側面、すなわちグラビアロール１４１の回転軸方向両端部にそれぞれ取り付けられている。
　図４に示すように、サイドプレート１４２ｄのグラビアロール１４１側の側面は、グラビアロール１４１の形状に沿った円弧形状となっており、グラビアロール１４１に圧接されている。 The chamber 142 has a side plate 142d made of resin. The side plates 142d are attached to both side surfaces of the chamber 142, that is, both ends of the gravure roll 141 in the rotation axis direction.
As shown in FIG. 4 , the side surface of the side plate 142 d on the side of the gravure roll 141 has an arc shape along the shape of the gravure roll 141 and is pressed against the gravure roll 141 .
　圧胴１４３は、図４に示すように、グラビアロール１４１との間で第二フィルムＷ２を挟持し、第二フィルムＷ２を搬送する。圧胴１４３は、第二フィルムＷ２をグラビアロール１４１に圧接させて、グラビアロール１４１の外周面に塗布されたポリオール組成物（Ｙ）を第二フィルムＷ２に転写する。
　一般的にミスティングは、ポリオール組成物（Ｙ）がロール間を転写により移動する際に発生する。本実施態様であれば、ポリオール組成物（Ｙ）のミスティングは、グラビアロール１４１と圧胴１４３とが圧接された付近で発生する。ミスティングが発生する場合には、ミスティングの発生を抑えるために、各ロールの回転速度および第二フィルムＷ２の搬送速度を下げる必要がある。しかし、第二フィルムＷ２の搬送速度を下げると、積層フィルム１１ａの生産効率が低下する。
　本実施形態では、ポリオール組成物（Ｙ）として、特定の伸長粘度を有する組成物を用いることにより、ミスティングの発生を抑制できる。その結果、優れた特性を有する積層フィルム１１ａを効率よく製造できる。 As shown in FIG. 4, the impression cylinder 143 holds the second film W2 between itself and the gravure roll 141, and conveys the second film W2. The impression cylinder 143 presses the second film W2 against the gravure roll 141 to transfer the polyol composition (Y) applied to the outer peripheral surface of the gravure roll 141 to the second film W2.
Generally, misting occurs when the polyol composition (Y) moves between rolls due to transfer. In this embodiment, the misting of the polyol composition (Y) occurs in the vicinity of the pressure contact between the gravure roll 141 and the impression cylinder 143 . If misting occurs, it is necessary to reduce the rotation speed of each roll and the conveying speed of the second film W2 in order to suppress the occurrence of misting. However, when the conveying speed of the second film W2 is lowered, the production efficiency of the laminated film 11a is lowered.
In the present embodiment, by using a composition having a specific elongational viscosity as the polyol composition (Y), the occurrence of misting can be suppressed. As a result, the laminated film 11a having excellent properties can be efficiently manufactured.
　塗工液タンク１４４は、ポリオール組成物（Ｙ）を貯留する容器である。図４に示すように、塗工液タンク１４４は、配管を介して、チャンバー１４２にポリオール組成物（Ｙ）を流入させるポンプ１４５に接続されている。また、塗工液タンク１４４は、配管を介して、チャンバー１４２と接続されている。これにより、チャンバー１４２の貯留部１４２ａからオーバーフローしたポリオール組成物（Ｙ）は、塗工液タンク１４４に回収されるようになっている。 The coating liquid tank 144 is a container that stores the polyol composition (Y). As shown in FIG. 4, the coating liquid tank 144 is connected via a pipe to a pump 145 for flowing the polyol composition (Y) into the chamber 142 . Also, the coating liquid tank 144 is connected to the chamber 142 via a pipe. As a result, the polyol composition (Y) overflowing from the reservoir 142 a of the chamber 142 is recovered in the coating liquid tank 144 .
　ポンプ１４５は、配管を介して、塗工液タンク１４４及びチャンバー１４２に接続されている。ポンプ１４５は、塗工液タンク１４４に貯留されているポリオール組成物（Ｙ）をチャンバー１４２の貯留部１４２ａに供給する。ポンプ１４５としては、例えばサインポンプを用いることができる。 The pump 145 is connected to the coating liquid tank 144 and the chamber 142 via piping. The pump 145 supplies the polyol composition (Y) stored in the coating liquid tank 144 to the reservoir 142 a of the chamber 142 . A sine pump, for example, can be used as the pump 145 .
　温度調節機１４６は、塗工液タンク１４４に貯留されているポリオール組成物（Ｙ）の温度を調整する。これにより、ポリオール組成物（Ｙ）の温度を一定に保ち、ポリオール組成物（Ｙ）の粘度を安定化する。温度調節機１４６は、例えば、熱媒体である水をヒーターで加熱して、塗工液タンク１４４に貯留されたポリオール組成物（Ｙ）の周囲を循環させる水用調温機である。 The temperature controller 146 adjusts the temperature of the polyol composition (Y) stored in the coating liquid tank 144. This keeps the temperature of the polyol composition (Y) constant and stabilizes the viscosity of the polyol composition (Y). The temperature controller 146 is, for example, a water temperature controller that heats water, which is a heat medium, with a heater and circulates around the polyol composition (Y) stored in the coating liquid tank 144 .
　貼合装置１５は、図２に示すように、貼合部１５１と、巻取部１５２とを備える。
　貼合部１５１は、ポリイソシアネート塗工部１２から送出された第一フィルムＷ１におけるポリイソシアネート組成物（Ｘ）の塗工面と、ポリオール塗工部１４から送出された第二フィルムＷ２におけるポリオール組成物（Ｙ）の塗工面とを貼り合わせる。巻取部１５２は、貼合部１５１によって貼り合わされた積層フィルム１１ａを巻き取る。 The bonding device 15 includes a bonding section 151 and a winding section 152, as shown in FIG.
The bonding portion 151 is a surface coated with the polyisocyanate composition (X) in the first film W1 delivered from the polyisocyanate coating portion 12 and a polyol composition in the second film W2 delivered from the polyol coating portion 14. The coated surface of (Y) is pasted together. The winding section 152 winds up the laminated film 11 a bonded by the bonding section 151 .
　貼合部１５１は、図２に示すように、一対のラミネートロールＲ１、Ｒ２を有している。ラミネートロールＲ１、Ｒ２は、第一フィルムＷ１と第二フィルムＷ２とを挟み込んで接合し、搬送する。２つのラミネートロールＲ１、Ｒ２は、図示しない温度調節部によって、外周面の温度が一定に保たれている。これにより、二液硬化型接着剤の硬化が安定化される。 The lamination section 151 has a pair of lamination rolls R1 and R2, as shown in FIG. The lamination rolls R1 and R2 sandwich and bond the first film W1 and the second film W2, and convey them. The two laminate rolls R1 and R2 are kept at a constant temperature on the outer peripheral surface by a temperature control unit (not shown). This stabilizes the curing of the two-component curing adhesive.
　貼合部１５１は、図２に示すように、第一フィルムＷ１と第二フィルムＷ２とを、対向配置された２つのラミネートロールＲ１、Ｒ２間に通過させて、ポリイソシアネート塗工部１２から送出された第一フィルムＷ１の塗工面と、ポリオール塗工部１４から送出された第二フィルムＷ２の塗工面とを接触させて貼り合わせる。貼合部１５１において、第一フィルムＷ１に塗布されたポリイソシアネート組成物（Ｘ）と、第二フィルムＷ２に塗布されたポリオール組成物（Ｙ）とが混合されることにより、二液硬化型接着剤の硬化が開始され、第一フィルムＷ１と第二フィルムＷ２とが貼り合わされ、固定される。 As shown in FIG. 2, the lamination unit 151 passes the first film W1 and the second film W2 between two laminate rolls R1 and R2 arranged opposite to each other, and sends them out from the polyisocyanate coating unit 12. The coated surface of the first film W1 fed from the first film W1 and the coated surface of the second film W2 delivered from the polyol coating unit 14 are brought into contact with each other and bonded together. In the bonding portion 151, the polyisocyanate composition (X) applied to the first film W1 and the polyol composition (Y) applied to the second film W2 are mixed to form a two-component curing adhesive. Curing of the agent is started, and the first film W1 and the second film W2 are attached and fixed.
　巻取部１５２は、貼合部１５１において第一フィルムＷ１と第二フィルムＷ２とが貼り合わされて形成された積層フィルム１１ａを巻き取る。 The winding section 152 winds up the laminated film 11a formed by bonding the first film W1 and the second film W2 together in the bonding section 151 .
［積層フィルムの製造方法］
　次に、本実施形態の積層フィルムの製造方法として、図２～図４に示す積層フィルムの製造装置１を用い、上述した本実施形態の二液硬化型接着剤を使用して図１に示す積層フィルム１１ａを製造する場合を例に挙げて説明する。
　本実施形態の積層フィルム１１ａの製造方法は、二液分別塗布工程と、接着剤層形成工程とを有する。本実施形態では、二液分別塗布工程と接着剤層形成工程とを連続的に行う。 [Method for producing laminated film]
Next, as a method for manufacturing the laminated film of the present embodiment, using the laminated film manufacturing apparatus 1 shown in FIGS. A case of manufacturing the laminated film 11a will be described as an example.
The method for manufacturing the laminated film 11a of the present embodiment includes a two-liquid separate coating process and an adhesive layer forming process. In this embodiment, the two-liquid separate application step and the adhesive layer forming step are performed continuously.
（二液分別塗布工程）
　二液分別塗布工程は、ポリイソシアネート（Ａ）を含み、伸長粘度が０．１～１０Ｐａ・ｓであるポリイソシアネート組成物（Ｘ）を第一フィルムＷ１に塗布する第一塗布工程と、ポリオール（Ｂ）を含み、かつ伸長粘度が０．１～１０Ｐａ・ｓであるポリオール組成物（Ｙ）を第二フィルムＷ２に塗布する第二塗布工程とからなる。本実施形態では、第１塗布工程と第２塗布工程とを同時に行う。 (Two-liquid separate application process)
The two-liquid separate application step includes a first application step of applying a polyisocyanate composition (X) containing a polyisocyanate (A) and having an elongational viscosity of 0.1 to 10 Pa s on the first film W1, and a polyol ( B) and a second coating step of coating the second film W2 with the polyol composition (Y) having an extensional viscosity of 0.1 to 10 Pa·s. In this embodiment, the first coating process and the second coating process are performed simultaneously.
「第１塗布工程」
　図２～図４に示す積層フィルムの製造装置１を用いて第１塗布工程を行う方法について説明する。
　まず、第１巻出部１１からポリイソシアネート塗工部１２に、第一フィルムＷ１を送出する。ポリイソシアネート塗工部１２において、各ロールを、図３において矢印で示す方向に回転させる。このことにより、液溜部１２０に貯留されているポリイソシアネート組成物（Ｘ）が、ドクターロール１２２の表面に塗布される。 "First coating process"
A method of performing the first coating step using the laminated film manufacturing apparatus 1 shown in FIGS. 2 to 4 will be described.
First, the first film W1 is delivered from the first unwinding section 11 to the polyisocyanate coating section 12 . In the polyisocyanate coating section 12, each roll is rotated in the direction indicated by the arrow in FIG. As a result, the polyisocyanate composition (X) stored in the liquid reservoir 120 is applied to the surface of the doctor roll 122 .
　本実施形態においては、図示しない温度調節部によって、液溜部１２０に貯留されているポリイソシアネート組成物（Ｘ）の温度を、２５℃～８０℃とすることが好ましく、２５℃～４０℃とすることがより好ましい。
　本実施形態において、ポリイソシアネート組成物（Ｘ）のせん断粘度は、４０℃において、３０００ｍＰａ・ｓ以下であることが好ましく、２０００ｍＰａ・ｓ以下であることがより好ましい。 In the present embodiment, the temperature of the polyisocyanate composition (X) stored in the liquid reservoir 120 is preferably adjusted to 25° C. to 80° C., preferably 25° C. to 40° C., by a temperature control unit (not shown). is more preferable.
In the present embodiment, the shear viscosity of the polyisocyanate composition (X) at 40° C. is preferably 3000 mPa·s or less, more preferably 2000 mPa·s or less.
　ドクターロール１２２に塗布されたポリイソシアネート組成物（Ｘ）は、メタリングロール１２３、コーティングロール１２４へと順次転写される。ポリイソシアネート塗工部１２の各ロールは、順次回転速度が大きくなるように設定されている。これにより、ポリイソシアネート組成物（Ｘ）の塗膜厚は徐々に小さくなり、コーティングロール１２４で所定の塗膜厚（塗布量）となるように調整される。 The polyisocyanate composition (X) applied to the doctor roll 122 is sequentially transferred to the metering roll 123 and the coating roll 124 . Each roll of the polyisocyanate coating section 12 is set so that the rotational speed increases sequentially. As a result, the coating thickness of the polyisocyanate composition (X) gradually decreases, and the coating roll 124 adjusts the coating thickness (coating amount) to a predetermined level.
　コーティングロール１２４に転写されたポリイソシアネート組成物（Ｘ）は、コーティングロール１２４とバッキングロール１２５との間を搬送される第一フィルムＷ１に転写される。これにより、第一フィルムＷ１にポリイソシアネート組成物（Ｘ）が塗布される。
　本実施形態においては、第一フィルムＷ１に塗布されるポリイソシアネート組成物（Ｘ）の塗布量は、０．５～３．０ｇ／ｍ２であることが好ましく、より好ましくは０．５～２．０ｇ／ｍ２である。
　ポリイソシアネート塗工部１２において、ポリイソシアネート組成物（Ｘ）の塗布された第一フィルムＷ１は、貼合装置１５に送出される。 The polyisocyanate composition (X) transferred to the coating roll 124 is transferred to the first film W<b>1 conveyed between the coating roll 124 and the backing roll 125 . Thereby, the polyisocyanate composition (X) is applied to the first film W1.
In this embodiment, the coating amount of the polyisocyanate composition (X) applied to the first film W1 is preferably 0.5 to 3.0 g/m 2 , more preferably 0.5 to 2 .0 g/ m2 .
In the polyisocyanate coating section 12 , the first film W<b>1 coated with the polyisocyanate composition (X) is delivered to the bonding device 15 .
「第２塗布工程」
　次に、図２～図４に示す積層フィルムの製造装置１を用いて第２塗布工程を行う方法について説明する。
　まず、第２巻出部１３からポリオール塗工部１４に、第二フィルムＷ２を送出する。ポリオール塗工部１４において、グラビアロール１４１および圧胴１４３を、図４において矢印で示す方向に回転させる。グラビアロール１４１の回転動作により、グラビアロール１４１の表面に、チャンバー１４２内のポリオール組成物（Ｙ）が第二フィルムＷ２に塗布される。 "Second coating process"
Next, a method of performing the second coating step using the laminated film manufacturing apparatus 1 shown in FIGS. 2 to 4 will be described.
First, the second film W2 is delivered from the second unwinding section 13 to the polyol coating section . In the polyol coating section 14, the gravure roll 141 and impression cylinder 143 are rotated in the directions indicated by the arrows in FIG. By rotating the gravure roll 141, the surface of the gravure roll 141 is coated with the polyol composition (Y) in the chamber 142 on the second film W2.
　本実施形態において、第二フィルムＷ２に塗布されるポリオール組成物（Ｙ）の塗布量は、０．５～３．０ｇ／ｍ２であることが好ましく、より好ましくは０．５～２．０ｇ／ｍ２である。 In this embodiment, the coating amount of the polyol composition (Y) applied to the second film W2 is preferably 0.5 to 3.0 g/m 2 , more preferably 0.5 to 2.0 g / m2 .
　本実施形態においては、温度調節機１４６によって、塗工液タンク１４４に貯留されているポリオール組成物（Ｙ）の温度を、２５℃～８０℃とすることが好ましく、２５℃～４０℃とすることがより好ましい。
　本実施形態においては、ポリオール組成物（Ｙ）の粘度は、グラビア塗工機に適した粘度とされている。 In the present embodiment, the temperature of the polyol composition (Y) stored in the coating liquid tank 144 is preferably adjusted to 25° C. to 80° C., preferably 25° C. to 40° C., by the temperature controller 146. is more preferable.
In this embodiment, the viscosity of the polyol composition (Y) is set to a viscosity suitable for a gravure coating machine.
　グラビアロール１４１の回転方向は、第二フィルムＷ２の搬送方向と同方向である正回転であってもよいし、第二フィルムＷ２の搬送方向と逆方向であるリバース回転であってもよい。本実施形態では、図４に示すように、グラビアロール１４１が、第二フィルムＷ２の搬送方向と逆方向に回転しながら、第二フィルムＷ２にポリオール組成物（Ｙ）を転写する。これにより、第二フィルムＷ２に塗布されたポリオール組成物（Ｙ）の外観を、縦筋、ロールの版目等のない良好なものとすることができる。
　ポリオール塗工部１４において、ポリオール組成物（Ｙ）の塗布された第二フィルムＷ２は、貼合装置１５に送出される。 The rotation direction of the gravure roll 141 may be forward rotation, which is the same direction as the transport direction of the second film W2, or reverse rotation, which is the opposite direction to the transport direction of the second film W2. In the present embodiment, as shown in FIG. 4, the gravure roll 141 transfers the polyol composition (Y) to the second film W2 while rotating in the direction opposite to the conveying direction of the second film W2. As a result, the appearance of the polyol composition (Y) applied to the second film W2 can be made good without vertical streaks, roll marks, and the like.
In the polyol coating section 14 , the second film W<b>2 coated with the polyol composition (Y) is delivered to the bonding device 15 .
（接着剤層形成工程）
　接着剤層形成工程では、第一フィルムＷ１と第二フィルムＷ２とを積層することにより、第一フィルムＷ１上に塗布されたポリイソシアネート組成物（Ｘ）と、第二フィルム上に塗布されたポリオール組成物（Ｙ）とを接触させて硬化反応させる。 (Adhesive layer forming step)
In the adhesive layer forming step, by laminating the first film W1 and the second film W2, the polyisocyanate composition (X) applied on the first film W1 and the polyol applied on the second film It is brought into contact with the composition (Y) to cause a curing reaction.
　貼合装置１５の貼合部１５１では、図２に示すように、第一フィルムＷ１と第二フィルムＷ２とが接触した状態で、対向配置された２つのラミネートロールＲ１、Ｒ２に挟持され、２つのラミネートロールＲ１、Ｒ２間を通過する。そして、２つのラミネートロールＲ１、Ｒ２からの圧力により、第一フィルムＷ１と第二フィルムＷ２とが貼り合わされる。 In the lamination unit 151 of the lamination device 15, as shown in FIG. 2, the first film W1 and the second film W2 are sandwiched between two lamination rolls R1 and R2 facing each other while being in contact with each other. pass between two laminate rolls R1, R2. Then, the first film W1 and the second film W2 are laminated together by the pressure from the two lamination rolls R1 and R2.
　本実施形態においては、２つのラミネートロールＲ１、Ｒ２の外周面の温度を、４０℃～８０℃とすることが好ましく、４０℃～６０℃とすることがより好ましい。
　２つのラミネートロールＲ１、Ｒ２から第一フィルムＷ１および第二フィルムＷ２への圧力は、例えば、３～３００ｋｇ／ｃｍ２とすることができる。
　本実施形態では、２つのラミネートロールＲ１、Ｒ２に挟持されることにより、ポリイソシアネート塗工部１２から送出された第一フィルムＷ１の塗工面と、ポリオール塗工部１４から送出された第二フィルムＷ２の塗工面とが接触する。その結果、第一フィルムＷ１に塗布されたポリイソシアネート組成物（Ｘ）と、第二フィルムＷ２に塗布されたポリオール組成物（Ｙ）とが混合され、二液硬化型接着剤の硬化が開始される。 In this embodiment, the temperature of the outer peripheral surfaces of the two laminate rolls R1 and R2 is preferably 40°C to 80°C, more preferably 40°C to 60°C.
The pressure from the two laminating rolls R1, R2 to the first film W1 and the second film W2 can be, for example, 3-300 kg/cm 2 .
In this embodiment, the coated surface of the first film W1 delivered from the polyisocyanate coating unit 12 and the second film delivered from the polyol coating unit 14 are sandwiched between the two lamination rolls R1 and R2. The coated surface of W2 contacts. As a result, the polyisocyanate composition (X) applied to the first film W1 and the polyol composition (Y) applied to the second film W2 are mixed, and curing of the two-component curable adhesive is started. be.
　二液硬化型接着剤が硬化することにより、第一フィルムＷ１と第二フィルムＷ２との間に接着剤層１０を有する積層フィルム１１ａが得られる。
　貼合部１５１で第一フィルムＷ１と第二フィルムＷ２とが貼り合わされることにより作製された積層フィルム１１ａは、巻取部１５２に搬送される。巻取部１５２に搬送された積層フィルム１１ａは、巻取部１５２に巻き取られる。 By curing the two-component curing adhesive, the laminated film 11a having the adhesive layer 10 between the first film W1 and the second film W2 is obtained.
The laminated film 11a produced by bonding the first film W1 and the second film W2 together in the bonding section 151 is conveyed to the winding section 152 . The laminated film 11 a conveyed to the winding section 152 is wound by the winding section 152 .
　本実施形態の積層フィルム１１ａの製造方法では、積層フィルム１１ａを製造する際のフィルム搬送速度（巻取部１５２における積層フィルム１１ａの巻き取り速度）を、例えば、３０～３００ｍ／ｍｉｎとすることができ、１００～２５０ｍ／ｍｉｎとすることが好ましい。本実施形態の積層フィルム１１ａの製造方法では、本実施形態の二液硬化型接着剤を用いて積層フィルム１１ａを製造するので、ポリイソシアネート組成物（Ｘ）およびポリオール組成物（Ｙ）によるミスティングの発生を抑制できる。このため、フィルム搬送速度を３０ｍ／ｍｉｎ以上にしても、二液硬化型接着剤のミスティングによって作業性が低下することがない。したがって、連続的に３０ｍ／ｍｉｎ以上の速いフィルム搬送速度で積層フィルムを効率よく製造できる。フィルム搬送速度が３００ｍ／ｍｉｎを超えると、ミスティング以外の塗工不具合、搬送自体の不具合、張り合わせ時の不具合等も起こり得る。このため、フィルム搬送速度は３００ｍ／ｍｉｎ以下とすることが好ましい。 In the method for manufacturing the laminated film 11a of the present embodiment, the film transport speed (the winding speed of the laminated film 11a in the winding unit 152) when manufacturing the laminated film 11a can be set to, for example, 30 to 300 m/min. preferably 100 to 250 m/min. In the method for producing the laminated film 11a of the present embodiment, since the laminated film 11a is produced using the two-component curing adhesive of the present embodiment, misting with the polyisocyanate composition (X) and the polyol composition (Y) can suppress the occurrence of Therefore, even if the film conveying speed is 30 m/min or more, the workability is not deteriorated due to the misting of the two-component curing adhesive. Therefore, the laminated film can be efficiently produced continuously at a high film transport speed of 30 m/min or more. If the film conveying speed exceeds 300 m/min, coating problems other than misting, problems during the transfer itself, problems during lamination, and the like may occur. Therefore, it is preferable to set the film transport speed to 300 m/min or less.
　本実施形態の製造方法により得られた積層フィルム１１ａは、貼合部１５１において第一フィルムＷ１と第二フィルムＷ２とを貼り合わせ、巻取部１５２に巻き取られた後、必要に応じて常温または加温下で３～４８時間保管し、エージングを行う。エージングを行うことによって、二液硬化型接着剤が十分に硬化し、接着剤層１０としての実用物性が発現する場合がある。
　本実施形態では、ポリイソシアネート組成物（Ｘ）およびポリオール組成物（Ｙ）が特定の伸長粘度を有する初期凝集力に優れる二液硬化型接着剤を用いるため、エージングの時間を短縮できる。また、二液硬化型接着剤の初期凝集力が高いことから、巻取部１５２に巻き取られた積層フィルム１１ａを、エージング前に簡易加工することが可能である。したがって、本実施形態の製造方法は、製造工程の選択の幅が広く、作業効率を向上させうる。 The laminated film 11a obtained by the manufacturing method of the present embodiment is obtained by bonding the first film W1 and the second film W2 together in the bonding section 151, and after being wound up by the winding section 152, is allowed to stand at room temperature as necessary. Alternatively, aging is performed by storing for 3 to 48 hours under heating. By performing aging, the two-component curing adhesive is sufficiently cured, and practical physical properties as the adhesive layer 10 may be exhibited.
In this embodiment, the aging time can be shortened because the polyisocyanate composition (X) and the polyol composition (Y) use a two-component curing adhesive having a specific elongational viscosity and excellent initial cohesive strength. Further, since the initial cohesive force of the two-component curing adhesive is high, the laminated film 11a wound on the winding section 152 can be easily processed before aging. Therefore, the manufacturing method of the present embodiment has a wide selection of manufacturing processes, and can improve work efficiency.
　本実施形態の積層フィルム１１ａの製造装置１は、伸長粘度が０．１～１０Ｐａ・ｓであるポリイソシアネート組成物（Ｘ）を第一フィルムＷ１に塗布するポリイソシアネート塗工部１２と、伸長粘度が０．１～１０Ｐａ・ｓであるポリオール組成物（Ｙ）を第二フィルムＷ２に塗布するポリオール塗工部１４と、第一フィルムＷ１のポリイソシアネート組成物（Ｘ）の塗工面と、第二フィルムＷ２のポリオール組成物（Ｙ）の塗工面とを貼り合わせる貼合装置１５とを有する。したがって、本実施形態の積層フィルム１１ａの製造装置１は、本実施形態の液硬化型接着剤を使用して、二液分別塗布工程を有する本実施形態の製造方法により積層フィルム１１ａを製造する場合に、好適に使用できる。 The manufacturing apparatus 1 of the laminated film 11a of the present embodiment includes a polyisocyanate coating unit 12 that applies a polyisocyanate composition (X) having an elongational viscosity of 0.1 to 10 Pa s to the first film W1, and an elongational viscosity A polyol coating portion 14 for applying a polyol composition (Y) having a value of 0.1 to 10 Pa s on the second film W2, a polyisocyanate composition (X) coated surface of the first film W1, and a second and a laminating device 15 for laminating the film W2 with the surface coated with the polyol composition (Y). Therefore, the manufacturing apparatus 1 of the laminated film 11a of the present embodiment uses the liquid-curable adhesive of the present embodiment and manufactures the laminated film 11a by the manufacturing method of the present embodiment having a two-liquid separate application process. can be preferably used.
　本実施形態の積層フィルム１１ａの製造装置１においては、ポリイソシアネート塗工部１２が、伸長粘度が０．１～１０Ｐａ・ｓであるポリイソシアネート組成物（Ｘ）を第一フィルムＷ１に塗布するものであり、ポリオール塗工部１４が、伸長粘度が０．１～１０Ｐａ・ｓであるポリオール組成物（Ｙ）を第二フィルムＷ２に塗布するものである。このため、本実施形態の積層フィルム１１ａの製造装置１では、第一フィルムＷ１のポリイソシアネート組成物（Ｘ）の塗工面と、第二フィルムＷ２のポリオール組成物（Ｙ）の塗工面とを貼り合わせる貼合装置において、二液硬化型接着剤のミスティングが発生しにくい。よって、本実施形態の積層フィルム１１ａの製造装置１を用いることにより、連続的に速いフィルム搬送速度で、効率よく積層フィルム１１ａを製造できる。 In the manufacturing apparatus 1 of the laminated film 11a of the present embodiment, the polyisocyanate coating unit 12 applies the polyisocyanate composition (X) having an extensional viscosity of 0.1 to 10 Pa s to the first film W1. and the polyol coating section 14 applies the polyol composition (Y) having an extensional viscosity of 0.1 to 10 Pa·s to the second film W2. Therefore, in the manufacturing apparatus 1 of the laminated film 11a of the present embodiment, the polyisocyanate composition (X)-coated surface of the first film W1 and the polyol composition (Y)-coated surface of the second film W2 are attached. Misting of the two-component curable adhesive is less likely to occur in the pasting device. Therefore, by using the manufacturing apparatus 1 for the laminated film 11a of the present embodiment, the laminated film 11a can be efficiently produced at a continuously high film transport speed.
　本実施形態の積層フィルム１１ａの製造装置１においては、積層フィルム１１ａを製造する際におけるポリオール組成物（Ｙ）によるミスティングの発生を抑制できる。このため、ポリオール塗工部１４として、ポリオール組成物（Ｙ）の粘度等の選択の幅が広がるグラビアコーターを備えていてもよいし、ポリオール組成物（Ｙ）のミスティングが発生しやすいロールコーターを備えていてもよく、ポリオール塗工部１４におけるポリオール組成物（Ｙ）の塗布装置の選択肢を増やすことができる。ポリオール塗工部１４におけるポリオール組成物（Ｙ）の塗布装置として、グラビアコーターを選択する場合には、ポリオール組成物（Ｙ）の粘度が低く、ロールコーターでは液ダレ等の不具合を生じる場合であっても、液ダレを生じることがなく、塗布品質を向上させて高品質の積層フィルム１１ａを製造できる。また、グラビアコーターを用いることで、ポリオール塗工部１４の構成を簡素化でき、積層フィルム１１ａの製造装置を小型化できる。 In the manufacturing apparatus 1 of the laminated film 11a of the present embodiment, it is possible to suppress the occurrence of misting due to the polyol composition (Y) when manufacturing the laminated film 11a. For this reason, the polyol coating section 14 may be equipped with a gravure coater with a wide range of selection such as the viscosity of the polyol composition (Y), or a roll coater with which misting of the polyol composition (Y) is likely to occur. may be provided, and the options for the coating device for the polyol composition (Y) in the polyol coating section 14 can be increased. When a gravure coater is selected as the device for applying the polyol composition (Y) in the polyol coating section 14, the viscosity of the polyol composition (Y) is low and problems such as dripping may occur with a roll coater. However, dripping does not occur, and coating quality can be improved to manufacture a high-quality laminated film 11a. Moreover, by using a gravure coater, the configuration of the polyol coating section 14 can be simplified, and the manufacturing apparatus for the laminated film 11a can be miniaturized.
　本実施形態の積層フィルム１１ａの製造装置１においては、比較的粘度の高いポリイソシアネート組成物（Ｘ）を第一フィルムＷ１に塗布するポリイソシアネート塗工部１２において、ロールコーターを用いている。ロールコーターを用いることにより、ポリイソシアネート組成物（Ｘ）の粘度が比較的高い場合にも塗布を行うことが可能となり、ポリイソシアネート組成物（Ｘ）の材料の選択の幅が広がる。 In the manufacturing apparatus 1 of the laminated film 11a of the present embodiment, a roll coater is used in the polyisocyanate coating section 12 that applies the relatively high viscosity polyisocyanate composition (X) to the first film W1. By using a roll coater, it is possible to apply even when the viscosity of the polyisocyanate composition (X) is relatively high, and the range of selection of the material of the polyisocyanate composition (X) is widened.
　本実施形態の積層フィルム１１ａの製造方法は、伸長粘度が０．１～１０Ｐａ・ｓであるポリイソシアネート組成物（Ｘ）を第一フィルムＷ１に塗布する第一塗布工程と、伸長粘度が０．１～１０Ｐａ・ｓであるポリオール組成物（Ｙ）を第二フィルムＷ２に塗布する第二塗布工程とからなる二液分別塗布工程と、第一フィルムＷ１と第二フィルムＷ２とを積層することにより、第一フィルムＷ１上に塗布されたポリイソシアネート組成物（Ｘ）と、第二フィルムＷ２上に塗布されたポリオール組成物（Ｙ）とを接触させて硬化反応させる接着剤層形成工程とを有する。本実施形態の積層フィルム１１ａの製造方法は、二液分別塗布工程を有するため、ポリイソシアネート組成物（Ｘ）とポリオール組成物（Ｙ）とを混合する工程が不要である。このため、ポリイソシアネート組成物（Ｘ）とポリオール組成物（Ｙ）とを混合する工程を有する場合と比較して、作業性に優れる。また、ポリイソシアネート組成物（Ｘ）とポリオール組成物（Ｙ）とを混合しないため、二液硬化型接着剤のポットライフによる制限を受けることなく、硬化の速い本実施形態の二液硬化型接着剤を使用できる。 The method for producing the laminated film 11a of the present embodiment comprises a first coating step of applying the polyisocyanate composition (X) having an elongational viscosity of 0.1 to 10 Pa·s to the first film W1, and By laminating the first film W1 and the second film W2, and a two-liquid separate coating step consisting of a second coating step of applying the polyol composition (Y) of 1 to 10 Pa s to the second film W2. and an adhesive layer forming step of contacting the polyisocyanate composition (X) applied on the first film W1 and the polyol composition (Y) applied on the second film W2 to cause a curing reaction. . Since the method for producing the laminated film 11a of the present embodiment has a two-component separate application step, the step of mixing the polyisocyanate composition (X) and the polyol composition (Y) is not required. Therefore, the workability is excellent as compared with the case of having a step of mixing the polyisocyanate composition (X) and the polyol composition (Y). In addition, since the polyisocyanate composition (X) and the polyol composition (Y) are not mixed, there is no limitation due to the pot life of the two-component curing adhesive, and the two-component curing adhesive of the present embodiment, which cures quickly. drug can be used.
　本実施形態の積層フィルム１１ａの製造方法では、第一塗布工程において、伸長粘度が０．１～１０Ｐａ・ｓであるポリイソシアネート組成物（Ｘ）を第一フィルムに塗布し、第二塗布工程において、伸長粘度が０．１～１０Ｐａ・ｓであるポリオール組成物（Ｙ）を第二フィルムＷ２に塗布する。このため、本実施形態の積層フィルム１１ａの製造方法では、第一フィルム上に塗布されたポリイソシアネート組成物（Ｘ）と、第二フィルム上に塗布されたポリオール組成物（Ｙ）とを接触させる接着剤層形成工程において、二液硬化型接着剤のミスティングが発生しにくく、連続的に速いフィルム搬送速度で効率よく積層フィルムを製造できる。 In the method for producing the laminated film 11a of the present embodiment, in the first coating step, the polyisocyanate composition (X) having an elongational viscosity of 0.1 to 10 Pa s is applied to the first film, and in the second coating step , a polyol composition (Y) having an elongational viscosity of 0.1 to 10 Pa·s is applied to the second film W2. Therefore, in the method for producing the laminated film 11a of the present embodiment, the polyisocyanate composition (X) applied on the first film and the polyol composition (Y) applied on the second film are brought into contact. In the adhesive layer forming step, misting of the two-component curing adhesive is less likely to occur, and the laminated film can be efficiently produced at a continuously high film transport speed.
　上記実施形態では、ポリイソシアネート塗工部１２としてロールコーターを用いているが、ポリイソシアネート組成物（Ｘ）の粘度が低い場合等には、ポリイソシアネート塗工部１２としてグラビアコーターを用いてもよい。
　また、上記実施形態では、ポリオール塗工部１４としてグラビアコーターを用いているが、ポリオール組成物（Ｙ）の塗布が可能である場合には、ポリオール塗工部１４としてロールコーターを用いてもよい。 In the above-described embodiment, a roll coater is used as the polyisocyanate-coated portion 12, but when the viscosity of the polyisocyanate composition (X) is low, etc., a gravure coater may be used as the polyisocyanate-coated portion 12. .
Further, in the above-described embodiment, a gravure coater is used as the polyol-coated portion 14, but a roll coater may be used as the polyol-coated portion 14 when the polyol composition (Y) can be applied. .
　また、上記実施形態の積層フィルム１１ａの製造装置１におけるポリオール塗工部１４では、温度調節機１４６によって塗工液タンク１４４に貯留されたポリオール組成物（Ｙ）の温度を調節することとしたが、さらに、チャンバー１４２の貯留部１４２ａに貯留されているポリオール組成物（Ｙ）の温度、および／またはグラビアロール１４１の温度を調節してもよい。これにより、塗工時のポリオール組成物（Ｙ）の粘度をさらに安定させることができ、塗布品質および積層フィルム１１ａの品質をより一層向上させることができる。 Further, in the polyol coating section 14 in the manufacturing apparatus 1 for the laminated film 11a of the above embodiment, the temperature of the polyol composition (Y) stored in the coating liquid tank 144 is adjusted by the temperature controller 146. Furthermore, the temperature of the polyol composition (Y) stored in the storage section 142a of the chamber 142 and/or the temperature of the gravure roll 141 may be adjusted. Thereby, the viscosity of the polyol composition (Y) during coating can be further stabilized, and the coating quality and the quality of the laminated film 11a can be further improved.
　本実施形態では、ポリイソシアネート組成物（Ｘ）を第一フィルムＷ１に塗布するポリイソシアネート塗工部１２と、ポリオール組成物（Ｙ）を第二フィルムＷ２に塗布するポリオール塗工部１４と、第一フィルムＷ１と第二フィルムＷ２とを貼り合わせる貼合装置１５とを有する積層フィルム１１ａの製造装置１を用いて、二液分別塗布工程を有する製造方法により、積層フィルム１１ａを製造する場合を例に挙げて説明したが、積層フィルム１１ａは、例えば、以下に示す製造装置を用いて二液混合塗布工程を有する製造方法により製造してもよい。 In the present embodiment, the polyisocyanate coating section 12 that applies the polyisocyanate composition (X) to the first film W1, the polyol coating section 14 that applies the polyol composition (Y) to the second film W2, and the An example of manufacturing the laminated film 11a by a production method having a two-liquid separate application process using the laminated film 11a production apparatus 1 having the laminating device 15 for laminating the first film W1 and the second film W2. 1, the laminated film 11a may be manufactured by a manufacturing method having a two-liquid mixing coating process using the manufacturing apparatus shown below, for example.
　図５は、本実施形態の積層フィルムの製造に使用する製造装置の他の例を説明するための正面図である。
　図５に示す積層フィルムの製造装置１Ａは、上述した本実施形態の二液硬化型接着剤を用いて、ロールから巻き出した第一フィルムＷ１とロールから巻き出した第二フィルムＷ２とを貼り合わせて、第一フィルムＷ１と第二フィルムＷ２との間に接着剤層１０を形成し、ロール状に巻き取られた上述した本実施形態の積層フィルム１１ａを製造する装置である。 FIG. 5 is a front view for explaining another example of the manufacturing apparatus used for manufacturing the laminated film of this embodiment.
A laminated film manufacturing apparatus 1A shown in FIG. In addition, the apparatus forms the adhesive layer 10 between the first film W1 and the second film W2, and manufactures the laminated film 11a of the present embodiment, which is wound into a roll.
　図５に示す積層フィルムの製造装置１Ａは、図５に示すように、第１巻出部１１と、混合液塗工部１２Ａと、第２巻出部１３と、貼合装置１５とを備える。
　図５に示す積層フィルムの製造装置１Ａが、図２に示す積層フィルムの製造装置１と異なるところは、ポリイソシアネート塗工部１２に代えて混合液塗工部１２Ａが設けられているところと、図２に示す積層フィルムの製造装置１におけるポリオール塗工部１４がないところのみである。
　図５に示す積層フィルムの製造装置１Ａにおいて、図２に示す積層フィルムの製造装置１と同じ部材については、同じ符号を付し、説明を省略する。 The laminated film manufacturing apparatus 1A shown in FIG. 5 includes, as shown in FIG. .
5 differs from the laminated film manufacturing apparatus 1 shown in FIG. 2 in that a mixture coating section 12A is provided instead of the polyisocyanate coating section 12; It is only the portion without the polyol coating section 14 in the laminated film manufacturing apparatus 1 shown in FIG.
In the laminated film manufacturing apparatus 1A shown in FIG. 5, the same members as those in the laminated film manufacturing apparatus 1 shown in FIG.
　図５に示す積層フィルムの製造装置１Ａにおける混合液塗工部１２Ａが、図２に示す積層フィルムの製造装置１のポリイソシアネート塗工部１２とは異なるところは、第１巻出部１１から送出された第一フィルムＷ１に、本実施形態の二液硬化型接着剤のポリイソシアネート組成物（Ｘ）とポリオール組成物（Ｙ）との混合液を塗布するところである。
　図５に示す積層フィルムの製造装置１Ａには、二液硬化型接着剤のポリイソシアネート組成物（Ｘ）とポリオール組成物（Ｙ）とを混合する図示しない混合装置が設けられている。また、図５に示す積層フィルムの製造装置１Ａには、図２に示す積層フィルムの製造装置１のポリイソシアネート供給部に代えて、配管を介して混合装置に接続された図示しない混合液供給部が備えられている。 5 differs from the polyisocyanate coating unit 12 of the laminated film manufacturing apparatus 1 shown in FIG. A mixed solution of the polyisocyanate composition (X) and the polyol composition (Y) of the two-component curing adhesive of the present embodiment is applied to the first film W1 thus formed.
The laminated film manufacturing apparatus 1A shown in FIG. 5 is provided with a mixing device (not shown) for mixing the polyisocyanate composition (X) and the polyol composition (Y) of the two-component curing adhesive. Further, in the laminated film manufacturing apparatus 1A shown in FIG. 5, instead of the polyisocyanate supplying section of the laminated film manufacturing apparatus 1 shown in FIG. is provided.
　図５に示す積層フィルムの製造装置１Ａを用いて本実施形態の積層フィルム１１ａを製造する方法としては、例えば、以下に示す製造方法を用いることができる。
　まず、第１巻出部１１から混合液塗工部１２Ａに、第一フィルムＷ１を送出する。混合液塗工部１２Ａにおいて、各ロールを、図３において矢印で示す方向に回転させる。このことにより、液溜部１２０に貯留されているポリイソシアネート組成物（Ｘ）とポリオール組成物（Ｙ）との混合液が、ドクターロール１２２の表面に塗布される。 As a method for manufacturing the laminated film 11a of the present embodiment using the laminated film manufacturing apparatus 1A shown in FIG. 5, for example, the following manufacturing method can be used.
First, the first film W1 is delivered from the first unwinding section 11 to the mixed liquid coating section 12A. In the mixed liquid coating section 12A, each roll is rotated in the direction indicated by the arrow in FIG. As a result, the mixed liquid of the polyisocyanate composition (X) and the polyol composition (Y) stored in the liquid reservoir 120 is applied to the surface of the doctor roll 122 .
　本実施形態においては、図示しない温度調節部によって、液溜部１２０に貯留されている混合液の温度を、２５℃～８０℃とすることが好ましく、２５℃～４０℃とすることがより好ましい。
　本実施形態において、混合液のせん断粘度は、４０℃において、２０００ｍＰａ・ｓ以下であることが好ましく、１８００ｍＰａ・ｓ以下であることがより好ましい。
　本実施形態では、混合装置において、ポリオール組成物（Ｙ）とポリイソシアネート組成物（Ｘ）とが混合されることにより、二液硬化型接着剤の硬化が開始される。 In the present embodiment, the temperature of the mixed liquid stored in the liquid reservoir 120 is preferably adjusted to 25° C. to 80° C., more preferably 25° C. to 40° C., by a temperature control unit (not shown). .
In the present embodiment, the shear viscosity of the mixture at 40° C. is preferably 2000 mPa·s or less, more preferably 1800 mPa·s or less.
In the present embodiment, the polyol composition (Y) and the polyisocyanate composition (X) are mixed in the mixing device to initiate curing of the two-component curing adhesive.
　ドクターロール１２２に塗布された混合液は、メタリングロール１２３、コーティングロール１２４へと順次転写される。コーティングロール１２４に転写された混合液は、コーティングロール１２４とバッキングロール１２５との間を搬送される第一フィルムＷ１に転写される。これにより、第一フィルムＷ１に混合液が塗布される。
　本実施形態においては、第一フィルムＷ１に塗布される混合液の塗布量は、０．５～３．０ｇ／ｍ２であることが好ましく、より好ましくは０．５～２．０ｇ／ｍ２である。
　混合液塗工部１２Ａにおいて、混合液の塗布された第一フィルムＷ１は、図５に示すように、貼合装置１５に送出される。 The mixed liquid applied to the doctor roll 122 is sequentially transferred to the metering roll 123 and the coating roll 124 . The mixed liquid transferred to the coating roll 124 is transferred to the first film W<b>1 conveyed between the coating roll 124 and the backing roll 125 . Thereby, the mixed liquid is applied to the first film W1.
In this embodiment, the coating amount of the mixture applied to the first film W1 is preferably 0.5 to 3.0 g/m 2 , more preferably 0.5 to 2.0 g/m 2 . is.
The first film W1 coated with the mixed liquid in the mixed liquid coating section 12A is delivered to the bonding device 15 as shown in FIG.
　また、図５に示すように、第２巻出部１３からは、第二フィルムＷ２が送出され、貼合装置１５に送出される。
　貼合装置１５の貼合部１５１では、図５に示すように、第一フィルムＷ１の混合液が塗布された面と、第二フィルムＷ２とが接触した状態で、対向配置された２つのラミネートロールＲ１、Ｒ２に挟持され、２つのラミネートロールＲ１、Ｒ２間を通過する。そして、２つのラミネートロールＲ１、Ｒ２からの圧力により、第一フィルムＷ１と第二フィルムＷ２とが貼り合わされる。 Moreover, as shown in FIG.
In the laminating unit 151 of the laminating device 15, as shown in FIG. 5, two laminates are arranged facing each other in a state where the surface of the first film W1 coated with the liquid mixture is in contact with the second film W2. It is sandwiched between rolls R1 and R2 and passes between the two laminating rolls R1 and R2. Then, the first film W1 and the second film W2 are laminated together by the pressure from the two lamination rolls R1 and R2.
　本実施形態においては、２つのラミネートロールＲ１、Ｒ２の外周面の温度を、４０℃～８０℃とすることが好ましく、４０℃～６０℃とすることがより好ましい。
　２つのラミネートロールＲ１、Ｒ２から第一フィルムＷ１および第二フィルムＷ２への圧力は、例えば、３～３００ｋｇ／ｃｍ２とすることができる。 In this embodiment, the temperature of the outer peripheral surfaces of the two laminate rolls R1 and R2 is preferably 40°C to 80°C, more preferably 40°C to 60°C.
The pressure from the two laminating rolls R1, R2 to the first film W1 and the second film W2 can be, for example, 3-300 kg/cm 2 .
　二液硬化型接着剤が硬化することにより、第一フィルムＷ１と第二フィルムＷ２との間に接着剤層１０を有する積層フィルム１１ａが得られる。
　貼合部１５１で第一フィルムＷ１と第二フィルムＷ２とが貼り合わされることにより作製された積層フィルム１１ａは、巻取部１５２に搬送される。巻取部１５２に搬送された積層フィルム１１ａは、巻取部１５２に巻き取られる。 By curing the two-component curing adhesive, the laminated film 11a having the adhesive layer 10 between the first film W1 and the second film W2 is obtained.
The laminated film 11a produced by bonding the first film W1 and the second film W2 together in the bonding section 151 is conveyed to the winding section 152 . The laminated film 11 a conveyed to the winding section 152 is wound by the winding section 152 .
　本実施形態の積層フィルム１１ａの製造方法では、積層フィルム１１ａを製造する際のフィルム搬送速度（巻取部１５２における積層フィルム１１ａの巻き取り速度）を、例えば、３０～３００ｍ／ｍｉｎとすることができ、１００～２５０ｍ／ｍｉｎとすることが好ましい。本実施形態の積層フィルム１１ａの製造方法では、本実施形態の二液硬化型接着剤を用いて積層フィルム１１ａを製造するので、ポリオール組成物（Ｙ）を含有する成分である混合液によるミスティングを抑制できる。このため、フィルム搬送速度を３０ｍ／ｍｉｎ以上にしても、混合液のミスティングによって作業性が低下することがない。したがって、連続的に３０ｍ／ｍｉｎ以上の速いフィルム搬送速度で効率よく積層フィルムを製造できる。フィルム搬送速度が３００ｍ／ｍｉｎを超えると、ミスティング以外の塗工不具合、搬送自体の不具合、張り合わせ時の不具合等も起こり得る。このため、フィルム搬送速度は３００ｍ／ｍｉｎ以下とすることが好ましい。 In the method for manufacturing the laminated film 11a of the present embodiment, the film transport speed (the winding speed of the laminated film 11a in the winding unit 152) when manufacturing the laminated film 11a can be set to, for example, 30 to 300 m/min. preferably 100 to 250 m/min. In the method for producing the laminated film 11a of the present embodiment, since the laminated film 11a is produced using the two-component curing adhesive of the present embodiment, misting by the mixed liquid which is the component containing the polyol composition (Y) can be suppressed. Therefore, even if the film transport speed is 30 m/min or more, the misting of the mixed solution does not lower the workability. Therefore, the laminated film can be efficiently produced continuously at a high film transport speed of 30 m/min or more. If the film conveying speed exceeds 300 m/min, coating problems other than misting, problems during the transfer itself, problems during lamination, and the like may occur. Therefore, it is preferable to set the film transport speed to 300 m/min or less.
　本実施形態の積層フィルム１１ａは、本実施形態の二液硬化型接着剤を使用して製造するため、第二フィルムＷ２上にポリオール組成物（Ｙ）を含有する成分である混合液を塗布しても、ポリオール組成物（Ｙ）によるミスティングが発生しにくい。このため、本実施形態の積層フィルム１１ａは、二液混合塗布工程を有する製造方法を用いて、効率よく製造できる。 Since the laminated film 11a of the present embodiment is manufactured using the two-component curing adhesive of the present embodiment, the mixed liquid, which is a component containing the polyol composition (Y), is applied onto the second film W2. However, misting due to the polyol composition (Y) is less likely to occur. Therefore, the laminated film 11a of the present embodiment can be efficiently manufactured using a manufacturing method having a two-liquid mixing coating process.
　上述した実施形態では、二液分別塗布工程を有する製造方法として、フィルム上にポリオール組成物（Ｙ）のみを塗布する工程を含む二液分別塗布工程を有する製造方法を用いて、積層フィルム１１ａを製造する場合を例に挙げて説明したが、二液分別塗布工程を有する製造方法として、例えば、以下に示す（１）の方法または（２）の方法を用いてもよい。 In the above-described embodiment, the laminated film 11a is formed by using a manufacturing method having a two-component separate coating process including a step of coating only the polyol composition (Y) on the film as the manufacturing method having the two-component separate coating process. Although the case of manufacturing has been described as an example, the following method (1) or (2), for example, may be used as a manufacturing method having a two-liquid separate coating step.
（１）第一塗布工程において、ポリイソシアネート組成物とポリオール組成物との混合液を第一フィルム上に塗布し、第二塗布工程において、硬化促進剤を含む溶液を第二フィルムに塗布する。
（２）第一塗布工程において、ポリオール組成物の一部とポリイソシアネート組成物との混合液を第一フィルム上に塗布し、第二塗布工程において、ポリオール組成物の残部と硬化促進剤とを含む溶液を第二フィルムに塗布する。 (1) In the first application step, a mixed solution of the polyisocyanate composition and the polyol composition is applied onto the first film, and in the second application step, a solution containing a curing accelerator is applied onto the second film.
(2) In the first coating step, a mixture of a part of the polyol composition and the polyisocyanate composition is applied on the first film, and in the second coating step, the remainder of the polyol composition and the curing accelerator are applied. The solution containing is applied to the second film.
　以下、実施例により本発明をさらに具体的に説明する。なお、本発明は、以下の実施例のみに限定されない。以下の実施例において、断りのない限り、「部」「％」は質量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples. In addition, the present invention is not limited only to the following examples. In the following examples, "parts" and "%" are based on mass unless otherwise specified.
（ポリイソシアネート組成物（Ｘ－１））
［ポリイソシアネート（Ａ）の製造］
　撹拌機、温度計、窒素ガス導入管を備えたフラスコに、４，４－ジフェニルメタンジイソシアネート（以下、「ＭＤＩ」と略記する）；４１．９部と、２，４’－ＭＤＩ；１３．０部と、キシリレンジイソシアネート；０．１部とを反応容器内に仕込み、窒素ガス下で攪拌し、６０℃まで加熱した。このフラスコに、さらに数平均分子量４００の２官能のポリプロピレングリコール（以下、「ＰＰＧ」と略記する。）；２０．０部と、数平均分子量２０００の２官能ＰＰＧ；２５．０部とを、数回に分けて滴下し、８０℃で５～６時間攪拌してウレタン化反応させることにより、ポリイソシアネート（Ａ）からなるポリイソシアネート組成物（Ｘ－１）を得た。 (Polyisocyanate composition (X-1))
[Production of polyisocyanate (A)]
41.9 parts of 4,4-diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") and 13.0 parts of 2,4'-MDI were added to a flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube. and 0.1 part of xylylene diisocyanate were placed in a reaction vessel, stirred under nitrogen gas, and heated to 60°C. Into this flask, 20.0 parts of bifunctional polypropylene glycol having a number average molecular weight of 400 (hereinafter abbreviated as "PPG") and 25.0 parts of bifunctional PPG having a number average molecular weight of 2000 were A polyisocyanate composition (X-1) composed of the polyisocyanate (A) was obtained by adding dropwise in batches and stirring at 80° C. for 5 to 6 hours to cause a urethanization reaction.
　ポリイソシアネート（Ａ）について、ジ－ｎ－ブチルアミンを使用した滴定法により、イソシアネート含有率を測定した。その結果、１４質量％であった。
　また、ポリイソシアネート（Ａ）について、４０℃における溶融せん断粘度を測定した。その結果、１５００ｍＰａ・ｓであった。 The isocyanate content of polyisocyanate (A) was measured by a titration method using di-n-butylamine. As a result, it was 14% by mass.
Moreover, the melt shear viscosity at 40° C. was measured for the polyisocyanate (A). As a result, it was 1500 mPa·s.
（ポリイソシアネート組成物（Ｘ－２、Ｘ－３））
　ポリイソシアネート組成物Ｘ－２、Ｘ－３として、以下に示すものを用意した。
　Ｘ－２：２Ｋ－ＳＦ－２２０Ａ（ＤＩＣ株式会社製）、イソシアネート含有率（１４質量％）
　Ｘ－３：２Ｋ－ＳＦ－７００Ａ（ＤＩＣ株式会社製）、イソシアネート含有率（２１質量％） (Polyisocyanate composition (X-2, X-3))
As the polyisocyanate compositions X-2 and X-3, the following were prepared.
X-2: 2K-SF-220A (manufactured by DIC Corporation), isocyanate content (14% by mass)
X-3: 2K-SF-700A (manufactured by DIC Corporation), isocyanate content (21% by mass)
（ポリオール組成物（Ｙ－１）～（Ｙ－６））
　表１に記載されたポリオール（Ｂ）とポリアミン（Ｃ）と添加剤とを、表１に示す割合で混合し、ポリオール組成物（Ｙ－１）～（Ｙ－６）を得た。 (Polyol Compositions (Y-1) to (Y-6))
The polyol (B), polyamine (C) and additives shown in Table 1 were mixed in the proportions shown in Table 1 to obtain polyol compositions (Y-1) to (Y-6).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１中の略号は以下の通りである。
「ポリオール（Ｂ）」
　ひまし油：精製ひまし油（伊藤製油株式会社製、水酸基価１６０ｍｇＫＯＨ／ｇ、４０℃溶融せん断粘度２５０ｍＰａ・ｓ）
　Ｄ－１０００：ポリプロピレングリコール（三井化学ポリウレタン株式会社製、数平均分子量約１，０００、水酸基価１１２ｍｇＫＯＨ／ｇ、４０℃溶融せん断粘度１５０ｍＰａ・ｓ）アクトコールＤ－１０００
　ＴＥ－３６０：トリエタノールアミンプロポキシレーティッド
　ＥＸＣＥＮＯＬ４３０：ポリプロピレングリコール（ＡＧＣ株式会社製；官能基３、数平均分子量約４３０、水酸基価４００ｍｇＫＯＨ／ｇ、２５℃溶融せん断粘度３５０ｍＰａ・ｓ）
　ＥＤＰ－３００：Ｎ，Ｎ，Ｎ’，Ｎ’－テトラキス（２―ヒドロキシプロピル）エチレンジアミン(株式会社ＡＤＥＫＡ社製) Abbreviations in Table 1 are as follows.
"Polyol (B)"
Castor oil: Refined castor oil (manufactured by Ito Oil Co., Ltd., hydroxyl value 160 mgKOH/g, 40° C. melt shear viscosity 250 mPa s)
D-1000: Polypropylene glycol (manufactured by Mitsui Chemicals Polyurethanes, Inc., number average molecular weight of about 1,000, hydroxyl value of 112 mgKOH/g, 40° C. melt shear viscosity of 150 mPa s) Actcol D-1000
TE-360: triethanolamine propoxylated EXCENOL430: polypropylene glycol (manufactured by AGC; functional group 3, number average molecular weight of about 430, hydroxyl value of 400 mgKOH/g, 25°C melt shear viscosity of 350 mPa s)
EDP-300: N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine (manufactured by ADEKA Co., Ltd.)
「ポリアミン（Ｃ）」
　ＥＣ３１０：ポリオキシプロピレンポリアミン（ＢＡＳＦ社製）ＢａｘｘｄｕｒＥＣ３１０
「触媒」
　ε－カプロラクタム：２－オキソヘキサメチレンイミン（関東化学株式会社製）
　δ－バレロラクタム：テトラヒドロ－２Ｈ－ピラン－２－オン（関東化学株式会社製）
　ＤＢＴＤＬ：ジブチル錫ジラウレート（日東化成株式会社製）ネオスタンＵ－１００
　Ｂｉ－Ｚｎ：ネオデカン酸ビスマスとネオデカン酸亜鉛の混合触媒（Ｔｈｅ　Ｓｈｅｐｈｅｒｄ　Ｃｈｅｍｉｃａｌ　Ｃｏｍｐａｎｙ製）Ｂｉｃａｔ８１０８／Ｚ混合
「接着促進剤」
　ＯＦＳ－６０４０：３－グリシジルオキシプロピルトリメトキシシラン（東レダウコーニング株式会社製）
　ＫＢＭ９０３：３－アミノプロピルトリエトキシシラン（信越化学工業株式会社製） "Polyamine (C)"
EC310: Polyoxypropylene polyamine (manufactured by BASF) Baxxdur EC310
"catalyst"
ε-caprolactam: 2-oxohexamethyleneimine (manufactured by Kanto Chemical Co., Ltd.)
δ-valerolactam: tetrahydro-2H-pyran-2-one (manufactured by Kanto Chemical Co., Ltd.)
DBTDL: Dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.) Neostan U-100
Bi-Zn: mixed catalyst of bismuth neodecanoate and zinc neodecanoate (manufactured by The Shepherd Chemical Company) Bicat 8108/Z mixture "adhesion promoter"
OFS-6040: 3-glycidyloxypropyltrimethoxysilane (manufactured by Dow Corning Toray Co., Ltd.)
KBM903: 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
（ポリオール組成物（Ｙ－７）～（Ｙ－８）
　ポリオール成分Ｙ－８、Ｙ－９として、以下に示すものを用意した。
　Ｙ－７：ＨＡ－２３４Ｂ（ＤＩＣ株式会社製）、水酸基価：９０ｍｇＫＯＨ／ｇ
　Ｙ－８：ＨＡ－７００Ｂ（ＤＩＣ株式会社製）、水酸基価：１２０ｍｇＫＯＨ／ｇ (Polyol composition (Y-7) to (Y-8)
As the polyol components Y-8 and Y-9, the following were prepared.
Y-7: HA-234B (manufactured by DIC Corporation), hydroxyl value: 90 mgKOH / g
Y-8: HA-700B (manufactured by DIC Corporation), hydroxyl value: 120 mgKOH / g
　ポリオール組成物（Ｙ－１）～（Ｙ－８）に使用した材料について、以下に示す方法により、水酸基価またはアミン価を求めた。
　水酸基価は、ＪＩＳ－Ｋ００７０の水酸基価測定方法に準拠して求めた。
　アミン価は、ＡＳＴＭ　Ｄ２０７３のアミン価標準試験方法に準拠して求めた。
　そして、ポリオール組成物（Ｙ－１）～（Ｙ－８）に含まれる水酸基価とアミン価との合計を求めた。その結果を表１および表２に示す。 The hydroxyl value or amine value of the materials used in the polyol compositions (Y-1) to (Y-8) was determined by the method shown below.
The hydroxyl value was obtained according to the hydroxyl value measurement method of JIS-K0070.
The amine value was determined according to ASTM D2073 Amine Value Standard Test Method.
Then, the sum of the hydroxyl value and the amine value contained in the polyol compositions (Y-1) to (Y-8) was determined. The results are shown in Tables 1 and 2.
　ポリイソシアネート組成物（Ｘ－１）～（Ｘ－３）及びポリオール組成物（Ｙ－１）～（Ｙ－８）について、以下に示す方法により、伸長速度が４０００ｓ－１における伸長粘度を測定した。その結果を表２に示す。
　伸長粘度は、ＪＩＳ－７１９９（ＩＳＯ　１１４４３、ＡＳＴＭ　Ｄ　３８３５）に記載されたキャピラリレオメータ評価方法に準拠して測定した。
　具体的には、ツインキャピラリ型の装置（Ｇｏｔｔｆｅｒｔ社製；ＲＨＥＯＧＲＡＰＨ２０）を用い、長さ１０ｍｍ、直径０．５ｍｍのキャピラリダイと、長さ０．２５ｍｍ、直径０．５ｍｍのキャピラリダイとを用いて、温度４０℃、せん断速度１０００～３０００００ｓ－１で測定した見かけのせん断粘度（圧力）から、バーグレー補正を使用して圧力損失を除去し、真のせん断粘度を得た。そして、真のせん断粘度と圧力損失から、コグスウェル式を用いて伸長速度と対応した伸長粘度を求めた。 For the polyisocyanate compositions (X-1) to (X-3) and the polyol compositions (Y-1) to (Y-8), the elongational viscosity at an elongation speed of 4000 s -1 was measured by the method shown below. . Table 2 shows the results.
The elongational viscosity was measured according to the capillary rheometer evaluation method described in JIS-7199 (ISO 11443, ASTM D 3835).
Specifically, using a twin-capillary device (Gottfert; RHEOGRAPH20), a capillary die with a length of 10 mm and a diameter of 0.5 mm and a capillary die with a length of 0.25 mm and a diameter of 0.5 mm were used. , a temperature of 40° C. and a shear rate of 1000-300000 s −1 , the pressure drop was removed using the Bergley correction to obtain the true shear viscosity. Then, from the true shear viscosity and pressure loss, the elongation velocity and the corresponding elongation viscosity were determined using the Cogswell equation.
「実施例１～実施例７、比較例１～比較例３」
　ポリイソシアネート組成物（Ｘ－１）～（Ｘ－３）と、ポリオール組成物（Ｙ－１）～（Ｙ－８）とを、表２に示す割合で使用し、以下に示す方法により、図２～図４に示す製造装置を用いて、実施例１～実施例７、比較例１～比較例３の積層フィルムを、１００、１５０、２００、２５０ｍ／ｍｉｎのフィルム搬送速度でそれぞれ作製した。 "Examples 1 to 7, Comparative Examples 1 to 3"
Polyisocyanate compositions (X-1) to (X-3) and polyol compositions (Y-1) to (Y-8) were used in the proportions shown in Table 2, and the 2 to 4, laminated films of Examples 1 to 7 and Comparative Examples 1 to 3 were produced at film transport speeds of 100, 150, 200 and 250 m/min, respectively.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２中、ポリイソシアネート組成物（Ｘ－１）～（Ｘ－３）と、ポリオール組成物（Ｙ－１）～（Ｙ－８）との割合は、ポリイソシアネート組成物（Ｘ－１）～（Ｘ－３）の有するイソシアネート基と、ポリオール組成物（Ｙ－１）～（Ｙ－８）の有する水酸基価とアミン価との合計とのモル比［イソシアネート基／（水酸基価＋アミン価）］が、１．４～１．６の範囲となるようにした。表２中に、上記モル比をＮＣＯ過剰率として記載する。 In Table 2, the ratios of the polyisocyanate compositions (X-1) to (X-3) and the polyol compositions (Y-1) to (Y-8) are the polyisocyanate compositions (X-1) to The molar ratio of the isocyanate group of (X-3) to the sum of the hydroxyl value and amine value of the polyol compositions (Y-1) to (Y-8) [isocyanate group/(hydroxyl value + amine value) ] is in the range of 1.4 to 1.6. In Table 2, the molar ratio is described as the NCO excess.
　また、表２に記載したポリイソシアネート組成物の官能基量は、ポリイソシアネート組成物（Ｘ－１）～（Ｘ－３）の有するイソシアネート含有率（％）である。表２に記載したポリオール組成物の官能基量は、ポリオール組成物の水酸基価とアミン価との合計（ｍｇＫＯＨ/ｇ）である。 The functional group content of the polyisocyanate composition shown in Table 2 is the isocyanate content (%) of the polyisocyanate compositions (X-1) to (X-3). The functional group content of the polyol composition described in Table 2 is the sum of the hydroxyl value and amine value of the polyol composition (mgKOH/g).
　厚さ１２μｍの片面コロナ処理ＰＥＴフィルム（第一フィルム）におけるコロナ処理を行った面に、ポリイソシアネート組成物（Ｘ－１）～（Ｘ－３）のいずれかをロールコーターで塗布した（第一塗布工程）。第一塗布工程は、塗工液タンクに貯留されたポリイソシアネート組成物（Ｘ）の温度を４０℃として行った。
　第一塗布工程と同時に、厚さ２５μｍのアルミ蒸着ポリプロピレン（ＶＭＣＰＰ）フィルム（第二フィルム）のアルミ蒸着面に、ポリオール組成物（Ｙ－１）～（Ｙ－８）のいずれかをグラビアコーターで塗布した（第二塗布工程）。 One of the polyisocyanate compositions (X-1) to (X-3) was applied to the corona-treated surface of a 12 μm-thick single-sided corona-treated PET film (first film) with a roll coater (first coating process). In the first coating step, the temperature of the polyisocyanate composition (X) stored in the coating liquid tank was set to 40°C.
Simultaneously with the first coating step, any one of the polyol compositions (Y-1) to (Y-8) was applied to the aluminum-deposited surface of a 25 μm-thick aluminum-deposited polypropylene (VMCPP) film (second film) with a gravure coater. applied (second application step).
　第一塗布工程および第二塗布工程は、ポリイソシアネート組成物（Ｘ－１）～（Ｘ－３）とポリオール組成物（Ｙ－１）～（Ｙ－８）との塗布量の合計が、２．０ｇ／ｍ２となるように行った。
　第一塗布工程および第二塗布工程において、塗布中の第一塗工部および第二塗工部を目視で確認し、後述する基準によりミスティング性を評価した。 In the first coating step and the second coating step, the total coating amount of the polyisocyanate compositions (X-1) to (X-3) and the polyol compositions (Y-1) to (Y-8) is 2. 0 g/m 2 .
In the first coating step and the second coating step, the first coated portion and the second coated portion during coating were visually observed, and the misting properties were evaluated according to the criteria described later.
　そして、第一塗布工程および第二塗布工程から連続して、接着剤層形成工程を行った。接着剤層形成工程は、第一フィルムと第二フィルムとを積層することにより、第一フィルム上に塗布されたポリイソシアネート組成物（Ｘ－１）～（Ｘ－３）のいずれかと、第二フィルム上に塗布されたポリオール組成物（Ｙ－１）～（Ｙ－８）のいずれかとを接触させて硬化反応させることにより行った。 Then, the adhesive layer forming process was performed continuously from the first coating process and the second coating process. In the adhesive layer forming step, by laminating the first film and the second film, any of the polyisocyanate compositions (X-1) to (X-3) applied on the first film and the second It was carried out by contacting any one of the polyol compositions (Y-1) to (Y-8) coated on the film to cause a curing reaction.
　１００、１５０、２００、２５０ｍ／ｍｉｎのフィルム搬送速度で製造した実施例１～実施例７、比較例１～比較例３の積層フィルムについて、それぞれ下記の基準により、第一塗布工程および第二塗布工程におけるミスティング性を評価し、３以上を合格とした。その結果を表２に示す。
（ミスティング性評価）
４：第一塗工部と第二塗工部の両方においてミスティングが発生しない
３：第一塗工部と第二塗工部の両方においてミスティングが若干発生する
２：第一塗工部と第二塗工部の両方においてミスティングが発生する
１：第一塗工部と第二塗工部の両方においてミスティングが激しく発生する The laminated films of Examples 1 to 7 and Comparative Examples 1 to 3 produced at film transport speeds of 100, 150, 200, and 250 m/min were subjected to the first coating step and the second coating according to the following criteria, respectively. The misting property in the process was evaluated, and 3 or more was regarded as acceptable. Table 2 shows the results.
(Evaluation of misting property)
4: No misting occurs in both the first and second coating parts 3: Some misting occurs in both the first and second coating parts 2: First coating part 1: Severe misting occurs in both the first and second coating parts
　２００ｍ／ｍｉｎのフィルム搬送速度で製造した実施例１～実施例７、比較例１～比較例３の積層フィルムについて、それぞれ以下に示す方法により、初期凝集力の評価としてズリ強度を測定し、評価した。ズリ強度は、接着剤層形成工程の終了後、雰囲気温度２５℃で、３時間、６時間、１２時間又は２４時間経過させた後に、それぞれ測定した。その結果を表２に示す。 For the laminated films of Examples 1 to 7 and Comparative Examples 1 to 3 produced at a film transport speed of 200 m / min, the shear strength was measured and evaluated as an evaluation of the initial cohesive strength by the method described below. did. The shear strength was measured after 3 hours, 6 hours, 12 hours, or 24 hours at an ambient temperature of 25° C. after the adhesive layer forming step. Table 2 shows the results.
（ズリ強度の測定方法）
　積層フィルムを幅１０ｍｍ、長さ２００ｍｍの短冊状に切り出し、第一フィルム側の面から幅方向に第一フィルムのみ切断した。次いで、第一フィルムの切断位置から平面視で長さ方向に１０ｍｍの間隔をあけた位置で、積層フィルムを第二フィルム側の面から幅方向に第二フィルムのみ切断した。このことにより、第一フィルムの切断位置と第二フィルムの切断位置との間に、平面積１０ｍｍ２の接着剤層を有する試験片を得た。
　得られた試験片の長さ方向一端をクランプで保持し、他端を長さ方向に引張り速度５ｍｍ／分で、引張り試験機（オートグラフＡＧＳ－Ｊ、島津製作所社製）を用いて引っ張り、ズリ強度を測定した。 (Method for measuring shear strength)
The laminate film was cut into strips having a width of 10 mm and a length of 200 mm, and only the first film was cut in the width direction from the first film side surface. Then, only the second film was cut in the width direction from the second film side of the laminated film at a position spaced 10 mm in the length direction in plan view from the cutting position of the first film. This gave a test piece having an adhesive layer with a plane area of 10 mm 2 between the cutting position of the first film and the cutting position of the second film.
One end of the obtained test piece in the length direction is held by a clamp, and the other end is pulled in the length direction at a speed of 5 mm / min using a tensile tester (Autograph AGS-J, manufactured by Shimadzu Corporation), The shear strength was measured.
（初期凝集力評価）
　ズリ強度の評価は、下記の基準により行い、エージング時間の短縮になる５Ｎ／１０ｍｍ以上（３以上）を合格とした。
１：１Ｎ／１０ｍｍ未満
２：１Ｎ／１０ｍｍ以上、５Ｎ／１０ｍｍ未満
３：５Ｎ／１０ｍｍ以上、１０Ｎ／１０ｍｍ未満
４：１０Ｎ／１０ｍｍ以上 (Initial cohesion evaluation)
The shear strength was evaluated according to the following criteria, and 5 N/10 mm or more (3 or more), which shortened the aging time, was regarded as acceptable.
1: less than 1 N/10 mm 2: 1 N/10 mm or more, less than 5 N/10 mm 3: 5 N/10 mm or more, less than 10 N/10 mm 4: 10 N/10 mm or more
　表２に示すように、ポリイソシアネート組成物（Ｘ）およびポリオール組成物（Ｙ）の伸長粘度が０．１～１０Ｐａ・ｓである実施例１～実施例７については、フィルム搬送速度が２５０ｍ／ｍｉｎという高速であっても、ミスティングが発生せず、良好な作業性が維持された。 As shown in Table 2, for Examples 1 to 7 in which the polyisocyanate composition (X) and the polyol composition (Y) had extensional viscosities of 0.1 to 10 Pa s, the film transport speed was 250 m/ Even at a high speed of min, misting did not occur and good workability was maintained.
　一方、ポリイソシアネート組成物（Ｘ）の伸長粘度が１０Ｐａ・ｓ超である比較例１、ポリオール組成物（Ｙ）の伸長粘度が１０Ｐａ・ｓ超である比較例２では、フィルム搬送速度が１００ｍ／ｍｉｎであっても、ミスティングが若干発生した。また、ポリイソシアネート組成物（Ｘ）およびポリオール組成物（Ｙ）伸長粘度が１０Ｐａ・ｓ超である比較例３では、フィルム搬送速度が１００ｍ／ｍｉｎであっても、ミスティングが発生した。 On the other hand, in Comparative Example 1 in which the polyisocyanate composition (X) had an elongational viscosity of more than 10 Pa s, and in Comparative Example 2 in which the polyol composition (Y) had an elongational viscosity of more than 10 Pa s, the film transport speed was 100 m/ Even at min, some misting occurred. In addition, in Comparative Example 3 in which the polyisocyanate composition (X) and the polyol composition (Y) had extensional viscosities of more than 10 Pa·s, misting occurred even when the film transport speed was 100 m/min.
　これらの結果から、ポリイソシアネート組成物（Ｘ）およびポリオール組成物（Ｙ）の伸長粘度が０．１～１０Ｐａ・ｓであることにより、ミスティングの発生を抑制でき、良好な作業性が得られることが確認できた。このことから、ポリイソシアネート組成物（Ｘ）およびポリオール組成物（Ｙ）の伸長粘度が０．１～１０Ｐａ・ｓであることにより、生産効率を向上させることが可能であることが分かった。 From these results, when the extensional viscosity of the polyisocyanate composition (X) and the polyol composition (Y) is 0.1 to 10 Pa s, the occurrence of misting can be suppressed and good workability can be obtained. I was able to confirm that. From this, it was found that the production efficiency can be improved by setting the extensional viscosity of the polyisocyanate composition (X) and the polyol composition (Y) to 0.1 to 10 Pa·s.
　また、表２から明らかなように、実施例１～実施例７では、接着剤層形成工程の終了後、３時間経過した後であっても１０Ｎ／１０ｍｍ以上の高いズリ強度が得られた。このことから、実施例１～実施例７では、接着剤層形成工程の終了後、早期にズリ強度が立ち上がり、高い初期凝集力が認められる。 In addition, as is clear from Table 2, in Examples 1 to 7, a high shear strength of 10 N/10 mm or more was obtained even after 3 hours had elapsed after the adhesive layer forming step was completed. From this, in Examples 1 to 7, the shear strength rises early after the end of the adhesive layer forming process, and a high initial cohesive strength is observed.
　一方、比較例１では、接着剤層形成工程の終了後、２４時間経過した後であってもズリ強度が１Ｎ／１０ｍｍ未満であった。また、比較例２では、接着剤層形成工程の終了後、１２時間経過した後であってもズリ強度が１０Ｎ／１０ｍｍ未満であった。また、比較例３では、接着剤層形成工程の終了後、２４時間経過した後であってもズリ強度が５Ｎ／１０ｍｍ未満であった。このことから、比較例１～比較例３では、早期にズリ強度が上がらず、実施例１～実施例７と比較して、初期凝集力に劣ることが確認できた。 On the other hand, in Comparative Example 1, the shear strength was less than 1 N/10 mm even after 24 hours had passed since the end of the adhesive layer forming process. Moreover, in Comparative Example 2, the shear strength was less than 10 N/10 mm even after 12 hours had passed since the end of the adhesive layer forming step. Moreover, in Comparative Example 3, the shear strength was less than 5 N/10 mm even after 24 hours had passed since the end of the adhesive layer forming step. From this, it was confirmed that in Comparative Examples 1 to 3, the shear strength did not increase at an early stage, and the initial cohesive strength was inferior to that in Examples 1 to 7.
　上記のことから、本発明の二液硬化型接着剤を用いて得られた積層フィルムは、初期凝集力に優れ、その製造時にミスティングが発生し難いものであって、優れた特性を有すると共に効率よく製造できる。 From the above, the laminated film obtained using the two-component curing adhesive of the present invention has excellent initial cohesive strength, is less prone to misting during its production, and has excellent properties. It can be manufactured efficiently.
　１：積層フィルムの製造装置、１０：接着剤層、１１：第１巻出部、１１ａ：積層フィルム、１２：ポリイソシアネート塗工部（第一塗工部）、１３：第２巻出部、１４：ポリオール塗工部（第二塗工部）、１５：貼合装置、１１１：フィルム装着部、１２０：液溜部、１２１：アプリケーションロール、１２２：ドクターロール、１２３：メタリングロール、１２４：コーティングロール、１２５：バッキングロール、１２６：堰板、１３１：フィルム装着部、１４１：グラビアロール、１４２：チャンバー、１４２ａ：貯留部、１４２ｂ：ドクターブレード、１４２ｃ：シールプレート、１４２ｄ：サイドプレート、１４３：圧胴、１４４：塗工液タンク、１４５：ポンプ、１４６：温度調節機、１５１：貼合部、１５２：巻取部、Ｒ１、Ｒ２：ラミネートロール、Ｗ１：第一フィルム、Ｗ２：第二フィルム。 1: laminated film manufacturing apparatus, 10: adhesive layer, 11: first unwinding section, 11a: laminated film, 12: polyisocyanate coating section (first coating section), 13: second unwinding section, 14: Polyol coating part (second coating part), 15: Bonding device, 111: Film mounting part, 120: Liquid reservoir part, 121: Application roll, 122: Doctor roll, 123: Metering roll, 124: Coating roll, 125: backing roll, 126: barrier plate, 131: film mounting part, 141: gravure roll, 142: chamber, 142a: storage part, 142b: doctor blade, 142c: seal plate, 142d: side plate, 143: Impression cylinder, 144: Coating liquid tank, 145: Pump, 146: Temperature controller, 151: Bonding unit, 152: Winding unit, R1, R2: Lamination roll, W1: First film, W2: Second film .

Claims (4)

  1. 　ポリイソシアネート組成物（Ｘ）とポリオール組成物（Ｙ）との硬化反応を用いる二液硬化型接着剤であって、
    　前記ポリイソシアネート組成物（Ｘ）がポリイソシアネート（Ａ）を含み、
    　前記ポリオール組成物（Ｙ）がポリオール（Ｂ）を含み、
    　前記ポリイソシアネート組成物（Ｘ）および前記ポリオール組成物（Ｙ）の伸長粘度が０．１～１０Ｐａ・ｓである、二液硬化型接着剤。     A two-component curing adhesive that uses a curing reaction between a polyisocyanate composition (X) and a polyol composition (Y),
    The polyisocyanate composition (X) contains a polyisocyanate (A),
    The polyol composition (Y) contains a polyol (B),
    A two-component curing adhesive, wherein the polyisocyanate composition (X) and the polyol composition (Y) have extensional viscosities of 0.1 to 10 Pa·s.
  2. 　第一フィルムと第二フィルムとの間に接着剤層を有し、
    　前記接着剤層が請求項１に記載の二液硬化型接着剤の硬化物からなる、積層フィルム。     having an adhesive layer between the first film and the second film;
    A laminated film, wherein the adhesive layer comprises a cured product of the two-component curing adhesive according to claim 1 .
  3. 　ポリイソシアネート（Ａ）を含み、かつ伸長粘度が０．１～１０Ｐａ・ｓであるポリイソシアネート組成物（Ｘ）を第一フィルムに塗布する第一塗工部と、
    　ポリオール（Ｂ）を含み、かつ伸長粘度が０．１～１０Ｐａ・ｓであるポリオール組成物（Ｙ）を第二フィルムに塗布する第二塗工部と、
    　前記第一フィルムの前記ポリイソシアネート組成物（Ｘ）の塗工面と、前記第二フィルムの前記ポリオール組成物（Ｙ）の塗工面とを貼り合わせる貼合装置とを有する、積層フィルムの製造装置。     A first coating section that applies a polyisocyanate composition (X) containing a polyisocyanate (A) and having an elongational viscosity of 0.1 to 10 Pa s to the first film;
    a second coating section for coating a second film with a polyol composition (Y) containing a polyol (B) and having an extensional viscosity of 0.1 to 10 Pa s;
    An apparatus for producing a laminated film, comprising a lamination device for laminating the surface of the first film coated with the polyisocyanate composition (X) and the surface of the second film coated with the polyol composition (Y).
  4. 　ポリイソシアネート（Ａ）を含み、かつ伸長粘度が０．１～１０Ｐａ・ｓであるポリイソシアネート組成物（Ｘ）を第一フィルムに塗布する第一塗布工程と、
    　ポリオール（Ｂ）を含み、かつ伸長粘度が０．１～１０Ｐａ・ｓであるポリオール組成物（Ｙ）を第二フィルムに塗布する第二塗布工程とからなる二液分別塗布工程と、
    　前記第一フィルムと前記第二フィルムとを積層することにより、前記第一フィルム上に塗布された前記ポリイソシアネート組成物（Ｘ）と、前記第二フィルム上に塗布された前記ポリオール組成物（Ｙ）とを接触させて硬化反応させる接着剤層形成工程とを有する、積層フィルムの製造方法。     A first coating step of coating a first film with a polyisocyanate composition (X) containing a polyisocyanate (A) and having an elongational viscosity of 0.1 to 10 Pa s;
    A two-liquid separate application step comprising a second application step of applying a polyol composition (Y) containing a polyol (B) and having an elongational viscosity of 0.1 to 10 Pa s on a second film;
    By laminating the first film and the second film, the polyisocyanate composition (X) applied on the first film and the polyol composition (Y) applied on the second film ) and an adhesive layer forming step of contacting and curing reaction.
PCT/JP2021/005515 2021-02-15 2021-02-15 Two-component curing adhesive, laminated film, device for producing laminated film, and method for producing laminated film WO2022172448A1 (en)

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